Interface Vol. 25, No. 2, Summer 2016

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FROM THE EDITOR Published by: The Electrochemical Society (ECS) 65 South Main Street Pennington, NJ 08534-2839, USA Tel 609.737.1902 Fax 609.737.2743 www.electrochem.org

Industry 4.0

Co-Editors: Vijay Ramani, ramani@iit.edu; Petr Vanýsek, pvanysek@gmail.com

O

nly a few months ago, I had little notion there was a concept called Industry 4.0. I looked it up when it was mentioned in my own proposal, in its executive statement, supplied by the Office of Sponsored Projects. The proposal was, the preamble said, “poised to be aligned with the currently evolving area of Industry 4.0.” I imagined it was perhaps some accounting standard, superseding Industry 3.1, but I thought I better find out more before somebody actually asks. I signed up for a professional workshop on the topic. Listening to the presentation I quickly became convinced that a specter is haunting Europe — the specter of Industry 4.0. We quickly learned from the panel of experts what Industry 4.0 is not. It is not embedding every product with an internet connection, it is not even the ability of the various gadgets to communicate with each other; it is the inherent required connection of all manufacturing tools and processes. A good alternative name for Industry 4.0 is Internet of Things and Services. Its aim is to alter the way the whole manufacturing industry operates.

Whether the car assembly line would access how tall I am, what colors I like, and whether I take a German shepherd for a ride, was not mentioned. It was not denied either. The potential for loss of privacy was implied, as was the danger of interference or sabotage by an uninvited party. There is definitely a big component of data security and legislative overlay involved in the Industry 4.0 concept as well.

The name came from a high-technology strategy project funded by the German federal government, first mentioned at the 2011 technology fair in Hannover. Two years later, on April 8, 2013, at the same fair, a set of implementation recommendations was presented to the German federal government. The principles are (unlike the internet “for people,” the one we are currently using) intended for industrial production. The characteristic will be high customization and flexibility of mass production. It has six design principles: interoperability, virtualization, decentralization, real-time capability, service orientation, and modularity; each of them a big word, maybe scary to some and maybe off-putting to others. And the explanation is not easy. The better written descriptions of Industry 4.0 are all many pages long and they still seem to be lacking in clarity — in part because they are trying to describe even what is now barely anticipated. The concept envisions a “smart factory” that should be able to dynamically respond in real time to demands, regulate supply, grow or shrink in capabilities, or adjust in response to demand and utilize all kinds of data through interconnected systems.

The number four came from the notion that the dramatically new manufacturing concepts of Industry 4.0 represent the fourth industrial revolution. The zero after the dot, ostensibly adding an order of resolution, is a silliness attempting to make it more attractive to the digitally-addicted population. The first industrial revolution was a manufacturing transition increasingly using more energy (tied to proliferation of the steam engine), machine tools, and new inventions in chemistry. Textile was the dominant industry then. It spanned the era from about 1760 to about 1840, clearly an evolution in terms of historical events. The second industrial revolution evolved from the first. It is marked by adoption of steam for transport (railways and ships), and then it continued by factory electrification, invention of the assembly line, and introduction of automobiles and combustion engines. The third industrial revolution is meant to be the digital era of communication, which started in the 1980s, and in name it was introduced in the eponymous book by Jeremy Rifkin (Palgrave Macmillan, 2011), where an important spot is claimed, among others, for electrochemists through renewable electricity.

There are new jobs to be created by the Industry 4.0 transition and there are jobs to be lost, even though at the workshop, we learned that some of the new jobs are even “not known yet.”

It is hard to plan a school curriculum for that. Not surprisingly, some of the most threatened jobs are for data entry, cashiers, ticket sellers, tellers, etc. But it also includes machinists and toolmakers, presumably replaced by robots. The least threatened are retail managers, doctors (excluding dentists, though), and yes, on the 20th spot even writers, editors, and linguists.

While teachers (university and high school) are on the sixth spot of the least threatened (continued on next page)

Guest Editors: Mekki Bayachou, m.bayachou@csuohio. edu; James Burgess, JAMBURGESS@gru.edu Contributing Editors: Donald Pile, donald.pile@gmail.com Managing Editor: Annie Goedkoop, annie.goedkoop@electrochem.org Interface Production Manager: Dinia Agrawala, interface@electrochem.org Advertising Manager: Casey Emilius, casey.emilius@electrochem.org Advisory Board: Robert Kostecki (Battery), Sanna Virtanen (Corrosion), Durga Misra (Dielectric Science and Technology), Elizabeth PodlahaMurphy (Electrodeposition), Jerzy Ruzyllo (Electronics and Photonics), A. Manivannan (Energy Technology), Paul Gannon (High Temperature Materials), John Staser (Industrial Electrochemistry and Electrochemical Engineering), Uwe Happek (Luminescence and Display Materials), Slava Rotkin (Nanocarbons), Jim Burgess (Organic and Biological Electrochemistry), Andrew C. Hillier (Physical and Analytical Electrochemistry), Nick Wu (Sensor) Publisher: Mary Yess, mary.yess@electrochem.org Publications Subcommittee Chair: Yue Kuo Society Officers: Krishnan Rajeshwar, President; Johna Leddy, Senior Vice President; Yue Kuo, 2nd Vice President; Christina Bock, 3rd Vice President; James Fenton, Secretary; E. Jennings Taylor, Treasurer; Roque J. Calvo, Executive Director Statements and opinions given in The Electrochemical Society Interface are those of the contributors, and ECS assumes no responsibility for them.

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The Electrochemical Society Interface • Summer 2016 • www.electrochem.org All recycled paper. Printed in USA.

---------------FROM THE EDITOR -------------------------------------------------------------------------------------------------------------------------------------------------------------------------The new PAT-Chamber -----------------------Temperature controlled docking station --------Ready for up to 16 PAT-Cells or PAT-Cell-Press for pressure monitoring -------With data acquisition of cell current, cell voltage, --------half cell voltages, global temperature, --------individual cell pressure ---------------Compatible with all of today´s potentiostats and battery testers ------------------------------------------------------------------------------------(continued from previous page)

jobs, it gives more of a breathing room than a solace. It is up to academia, the academic, and applied researchers to formulate what will be important to teach and study in the next twenty years. Not surprisingly, most of the professions projected to be in demand have to do with computer networks, data management, and software programming. But there is also a call for expertise in law and legislative.

Without much doubt one research opportunity in our collective ECS expertise is what is now called “Big Data.” It refers to collecting huge amounts of digitized data, processing them, and deriving pertinent information. While manufacturing may have different aims, data processing and deriving information from various research endeavors is already reality. The pharmaceutical industry has been doing it for a while and a smart sensor network in a modern automobile is another example, where some parameters are derived through an algorithm, without even having the corresponding sensor installed. Open access to published literature will give increasingly an opportunity to analyze already published results (in particular, in data supplements).

The changes in employment structure are inevitably going to bring social changes as well. A shorter work week is predicted, although I recall that with the advent of personal computers in 1980 a four-day work week was promised by 2000. But in this scenario the shorter work week is also tied to planned unemployment, which considers required wealth redistribution, something akin to: From each according to his ability, to each according to his needs.

The initiative of Industry 4.0 that started in Germany is spreading throughout Europe. And it will have now official backing in the U.S. as well. As President Obama opened the Hannover Industrial Fair on April 24, 2016, he delivered a strong support for the Transatlantic Trade and Investment Partnership, which can, among others, help reap rewards of the Internet of Things.

Petr Vanýsek, Interface Co-Editor

http://orcid.org/0000-0002-5458-393X

4 The Electrochemical Society Interface • Summer 2016 • www.electrochem.org Discover our new pressure test cell for the PAT series: el-cell.com/products/test-cells/pat-chamber

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from the president

More Transitions: Déjà Vu All Over Again!

T

changes that have since occurred in the publication landscape? he last time I wrote in these For-profit organizations and the opening of floodgates from magazine pages was when countries like China have completely changed the rules of I was stepping down as the the game. We are at a juncture where it is either “Adapt or Editor and transitioning into the role Perish” (more than “Publish or Perish”). However, I have no of Vice President for this wonderful Society, which has been doubt that with its combined talent and brainpower that the the home for my professional life for close to four decades.

Society membership and staff boasts in its ranks, we will have Now, once again, I have the opportunity to write a column in this thing figured out. We have to wrestle back content that Interface as the Society President. This is my first such column has bled to other publication venues (and there are so many and hence, its title above, as I embark on a new “phase” excellent candidates that transition. I am excited, our publications are humbled, and yes, even a competing against); at little overwhelmed, when the same time, we should I think of the giants in the “Issues of sustainability, both in the continue our pre-eminent electrochemistry and solid way we do business, as well as in the position in core areas of state science communities way we live, will shape the strategies strength. who have been past leaders we adopt to meet the shifting sands in Initiatives such as of our Society. I have an Free the Science provide incredible opportunity ahead the publication, and more generally, a logical opportunity for of me that I shall try and in the R&D arenas.” our wonderful Society capture in the following to play a path-blazing paragraphs. and transformative role.

It is not a secret that The Issues of sustainability, Electrochemical Society both in the way we do business, as well as in the way we live, has done an incredibly good job of organizing meetings ever will shape the strategies we adopt to meet the shifting sands in since its inception. This is the place to be if you are engaged the publication, and more generally, in the R&D arenas. Other in the business of “pushing” or storing electrons. It is also a opportunities present themselves in the gray zone that separates venue where industry vendors showcase their products and R&D and technology translation. The Society has and should processes to a targeted audience. Students have always found continue to play a pivotal role in helping our community take a welcoming environment to publicize their work, and equally what they have developed in their R&D laboratories to the important, to network with their peers, listen to stalwarts speak marketplace. In the early history of this Society, sponsoring in their chosen area of specialization, or simply to kick back industry members such as Bell Laboratories fulfilled this role. and enjoy, whatever the meeting location has to offer, in the The more recent “experiments” we have jointly done with form of entertainment and amenities. I vividly recall my first socially-conscientious partners such as the Bill & Melinda ECS meeting (in Boston) as an impressionable postdoctoral Gates Foundation provide a logical roadmap to further such fellow from Colorado State University, where I had the leveraging opportunities. opportunity to listen to people like Mark Wrighton, Royce All the aspects discussed above are phase transitions in one Murray, and Rudy Marcus. They talked about their latest work way or the other, albeit perhaps not in a materials sense. Let in chemically-modified electrodes, photoelectrochemistry, and me end with soliciting and welcoming discussions with each electron transfer theory; these research topics were “hot” then, one of you—the constituents that the Society serves—and, and there was a sense of excitement and anticipation that ECS most importantly, stay tuned. was able to build on.

The publications side of the house has seen some good times and some challenging ones. The Society journal was simply the place to publish in areas such as not only the aforementioned ones, but also in areas such as electrochemical engineering, batteries and fuel cells, and corrosion. The solid Krishnan Rajeshwar state (the so-called “dry” side) was also thriving in areas ECS President related to oxide layers and devices based on silicon and other compound semiconductors. Who could have foreseen the

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

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Volume 72– S a n D i e g o , C a l i f o r n i a

from the San Diego meeting, May 29—June 2, 2016

The following issues of ECS Transactions are from symposia held during the San Diego meeting. All issues are available in electronic (PDF) editions, which may be purchased, beginning on May 20, 2016, by visiting www.electrochem.org/online-store.

Some issues are also available in CD/USB editions. Please visit the ECS website for all issue pricing and ordering information.

(All prices are in U.S. dollars; M = ECS member price; NM = nonmember price.)

Available Issues Vol. 72 Engineering Carbon Hybrids - Carbon Electronics 2 No. 1 CD/USB................... M $96.00, NM $119.00 Vol. 72 Dielectrics for Nanosystems 7: No. 2 Materials Science, Processing, Reliability, and Manufacturing -and- Solid State Topics General Session HC ................................M $97.00, NM $121.00 Vol. 72 More-than-Moore 3 No. 3 CD/USB................... M $96.00, NM $119.00

Vol. 72 Wide Bandgap Semiconductor Materials No. 5 and Devices 17 CD/USB.............................M $121.00, NM $151.00 Vol. 72 Solid-State Electronics and Photonics in No. 6 Biology and Medicine 3 CD/USB ............. M $96.00, NM $119.00 Vol. 72 Ionic and Mixed Conducting Ceramics 10 No. 7 CD/USB................... M $140.00, NM $176.00

Vol. 72 Silicon Compatible Materials, Processes, and Technologies No. 4 for Advanced Integrated Circuits and Emerging Applications 6 CD/USB..............................M $116.00, NM $145.00

Forthcoming Issues Joint General Session: Batteries and Energy Storage -and- Fuel Cells, Electrolytes, and Energy

SAN C01

Corrosion General Session

SAN D02

Chemical Mechanical Polishing 14

SAN A02

Future and Present Advanced Lithium Batteries and Beyond – a Symposium in the Honor of Prof. Bruno Scrosati

SAN D04

Plasma and Thermal Processes for Materials Modification, Synthesis and Processing

SAN A03

Large-Scale Energy Storage 7

SAN E01

Electrophoretic Deposition

SAN A04

Battery Modeling and Computation

SAN E02

SAN A05

Electrochemistry and Batteries for Safe and Low-cost Energy Storage

Three-Dimensional Electrodeposition and Electroless Deposition

SAN F01

SAN B01

Carbon Nanostructures for Energy Conversion

Industrial Electrochemistry and Electrochemical Engineering General Session

SAN H03

Properties and Applications of 2-Dimensional Layered Materials

SAN I01

State-of-the-Art Invited Tutorials on Model/Experiment Coupling in Low Temperature Fuel Cells

SAN A01

SAN B02 SAN B03

Carbon Nanostructures in Medicine and Biology Carbon Nanotubes - From Fundamentals to Devices

SAN K02

Bioelectrochemistry: Analysis and Fundamental Studies

AN L01

Physical and Analytical Electrochemistry, Electrocatalysis, and Photoelectrochemistry General Session

SAN L02

Electrocatalysis 8

SAN L03

Biological Fuel Cells 7

SAN L06

Ionic Liquids as Electrolytes

SAN L07

Renewable Fuels via Artificial Photosynthesis or Electrolysis

SAN M01

Sensors, Actuators, and Microsystems General Session

SAN M02

Medical and Point-of-Care Sensors

SAN Z01

General Society Student Poster Session

SAN Z02

Nanotechnology General Session featuring Nanoscale Luminescent Materials 4

SAN B04

Endofullerenes and Carbon Nanocapsules

SAN I03

Hydrogen and Oxygen Evolution Catalysis for Water Electrolysis 2

SAN B05

Fullerenes - Chemical Functionalization, Electron Transfer, and Theory

SAN I04

Mechano-Electro-Chemical Coupling in Energy Related Materials and Devices 2

SAN Z03

Grand Challenges in Energy Conversion and Storage

SAN B06

Graphene and Beyond: 2D Materials

SAN I05

Heterogeneous Functional Materials for Energy Conversion and Storage

SAN Z05

Sustainable Materials and Manufacturing

SAN Z06

Modeling: From Elucidation of Physical Phenomena to Applications in Design

SAN B07

Inorganic/Organic Nanohybrids for Energy Conversion

SAN B08

Porphyrins, Phthalocyanines, and Supramolecular Assemblies

SAN K01

12th Manuel M. Baizer Memorial Symposium on Organic Electrochemistry

Ordering Information To order any of these recently-published titles, please visit the ECS Digital Library, http://ecsdl.org/ECST/ Email: customerservice@electrochem.org

8

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

4/15/16

229th ECS Meeting

SAN DIEGO

Highlights from the 229th ECS Meeting

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ver 2,309 people from 30 countries attended the 229th ECS Meeting in San Diego, California, May 29 – June 2, 2016. This was ECS’s first return visit to San Diego since 1998. Participants could choose from over 2,200 presentations.

Plenary Session ECS President Daniel Scherson welcomed attendees to the meeting during Monday evening’s Plenary Session. In addition to wrapping up the first full day of technical sessions and honoring award winners, Scherson introduced everyone to what would be a major theme throughout the meeting: Free the Science.

“This is a monumental meeting for ECS,” Scherson said. “Today is the official launch of our Free the Science initiative.”

Free the Science ECS Executive Director Roque Calvo gave those in attendance a first look at the Society’s Free the Science initiative during the Plenary Session. Free the Science aims to provide complete open access to the ECS Digital Library – free for authors, readers, and libraries.

“The sciences we represent provides solutions to worldwide problems in energy, water, health, and general planet sustainability,” Calvo said. “It’s never been more important to advance our science, so I couldn’t be more excited about our future which will be propelled by the Free the Science initiative.”

Scientific publishing is a multi-billion dollar industry, but little of that money is reinvested in the scientists actually conducting the research. Fees associated with publishing and accessing papers often create barriers that inhibit the discoverability of research and ultimately the advancement of science. Free the Science seeks to remove these fees, so scientists can share their work with readers around the world, allowing more minds to think about and solve problems.

“Free the Science, when it is fully implemented, will be a remarkable legacy for ECS in the scientific publishing arena, but it

ECS Executive Director Roque Calvo spoke at the plenary session about the Society’s Free the Science initiative.

ECS President Dan Scherson presented the opening remarks at the 229th ECS Meeting.

will be fruitless if we don’t concentrate on what we are good at,” Calvo said. “That is exchanging information at meetings like this, recognizing achievements in our field, supporting young scientists, and offering educational programs. All of these things, along with your support of our journals, will allow ECS to successfully free the science and ultimately accelerate progress.”

The ECS Lecture “Seeing, Measuring and Understanding Vesicular Exocytosis of Neurotransmitters,” was the title of the ECS Lecture given

by Christian Amatore, Director of Research at École Normale Supérieure and CNRS. His talk focused on obtaining and investigating chromaffin cells, which release adrenaline into the blood stream. The goal of Amatore’s work is essentially to derive topological, energetic, and dynamic information about vesicular exocytotic phenomena.

Christian Amatore gave the ECS Lecture at the plenary session.

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Science for Solving Society’s Problems Challenge: Grant Winners In its first Science for Solving Society’s Problems Challenge in 2014, ECS partnered with the Bill & Melinda Gates Foundation to leverage the brainpower of many scientists in electrochemistry and solid state science and technology. The grantees of that challenge presented their work during the 229th ECS Meeting and addressed how they are applying electrochemistry to global issues in water, sanitation, and hygiene that affect more than two billion people worldwide.

“This program has infused our work with more added energy and purpose,” said E.J. Taylor, symposia moderator and Treasurer of ECS. “This has been very exciting for sustainability issues.”

Through the program, ECS awarded over $360,000 of seed funding to seven innovative research projects. Grant winners highlighted their work through a general overview, oral presentations, and a poster session.

Carl Hensman of the Bill & Melinda Gates Foundation delivered the keynote address for the symposia, where he discussed the risks associated with innovation and how we can detect and break down roadblocks.

“I always challenge people who say it’s not possible,” Hensman said. “People thought cars were pointless: too expensive, too complex, no possibility for a fueling network. But everything comes with risk, and we have the potential to reduce that risk.”

Presenters included: • Eric Wachsman, University of Maryland, “Sustainable Water Treatment Using an SOFC-Based Combined Heat and Power System” • Gemma Reguera, Michigan State University, “SPEED: Sanitation and Processing for Energy with Electrochemical Devices” • Plamen Atanassov, University of New Mexico, “Self-Powered Supercapacitive Microbial Fuel Cell” • Neus Sabaté, Institut de Microelectrónica de Barcelona, “powerPAD: Non-Toxic Capillary-Based Flow Battery for Single Use Applications” • Jörg Kretzschmar on behalf of Falk Harnisch, Helmholtz Centre for Environment Research, “eLatrines: Development of a Fully Cardboard based Microbial Fuel Cell for Pit Latrines” • Luis Godinez, CIDETEQ, “In-Situ Electrochemical Generation of the Fenton Reagent for the Treatment of Human Wastewater” • Gerardine Botte, Ohio University, “Electrochemical Disinfection of Wastewater Using Urea Electrolysis”

Award Highlights

Ralph E. White (right), recipient of the Vittorio de Nora Award, is shown here with his wife, Marjorie Nicholson (left).

The Vittorio de Nora Award was presented to Ralph E. White.

White is currently a professor at the University of South Carolina.

His work focuses on fuel cells, batteries, electrodeposition, and corrosion. The Vittorio de Nora Award was established in 1971 to recognize distinguished contributions to the field of electrochemical engineering and technology.

The Henry B. Linford Award for Distinguished Teaching was presented to John R. Scully. Scully’s research focuses on standards of living and safety through understanding the scientific mechanisms of corrosion while preventing and protecting against corrosion phenomena. Scully was unable to attend the meeting and will be delivering his award address during PRiME 2016. The Henry B. Linford Award for Distinguished Teaching was established in 1981 for excellence in teaching in subject areas of interest to the Society.

The Leadership Circle Award recognized Princeton Applied Research/Solartron Analytical at the gold level and Faraday Technology, Inc., Metrohm USA, and Pine Research Instrumentation at the silver level.

There were eight Division awards: • Electronics and Photonics Division Award was presented to Michael Shur of Rensselaer Polytechnic Institute.

• Energy Technology Division Research Award was presented to Thomas Zawodzinski of the University of TennesseeKnoxville and Oak Ridge National Laboratory.

• Energy Technology Division Supramaniam Srinivasan Young Investigator Award was presented to Prabeer Barpanda of the Indian Institute of Science.

• Energy Technology Division Graduate Student Award was presented to Matthew Genovese of the University of Toronto.

• Industrial Electrochemistry and Electrochemical Engineering Division Student Achievement Award was presented to Regis P. Dowd, Jr. of the University of Kansas.

• High Temperature Materials Division J. Bruce Wagner, Jr. Award was presented to Sean Bishop of MIT. • Nanocarbons Division SES Young Investigator Award was presented to Jiayan Luo of Tianjin University.

• Organic and Biological Electrochemistry Division Manuel M. Baizer Award was presented to Kevin The grantees of the Science for Solving Society’s Problems Challenge, from left to right: Luiz Godinez, Jörg Moeller of Washington University in Kretzchmar (presented for Falk Harnisch), Gemma Reguera, Juan Pablo Esquivel, Neus Sabate, Erik St. Louis.

Kjeang, Eric Wachsman, Gerardine Botte, Plamen Atanassov, and Carl Hensman.

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The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

ECS President Dan Scherson (center) with Brian Sayers (left) and Rob Sides (right) from Princeton Applied Research/Solartron Analytical, winner of the gold level Leadership Circle Award.

Sean Bishop, winner of the High Temperature Materials Division J. Bruce Wagner, Jr. Award.

ECS President Dan Scherson (center) with Ritesh Vyas (left) and Michael Kubicsko (right) from Metrohm USA, winner of the silver level Leadership Circle Award.

Prabeer Barpanda, winner of the Energy Technology Division Supramaniam Srinivasan Young Investigator Award.

ECS President Dan Scherson (left) with E. Jennings Taylor (right) from Faraday Technology, Inc., winner of the silver level Leadership Circle Award.

Matthew Genovese, winner of the Energy Technology Division Graduate Student Award. (continued on next page)

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Award Highlights (continued from previous page)

Thomas Zawodzinski (left) was presented with the Energy Technology Division Research Award by Scott Calabrese Barton (right), Division Chair.

Regis P. Dowd, Jr. (left), winner of the Industrial Electrochemisty and Electrochemical Engineering Division Student Achievement Award, with John Staser (right), Division Secretary/Treasurer.

Kevin Moeller, winner of the Organic and Biological Electrochemistry Division Manuel M. Baizer Award.

Jiayan Luo (left) was presented with the Nanocarbons Division SES Young Investigator Award by R. Bruce Weisman (right), Division Chair.

Free the Science 5K The weather was perfect for the Free the Science 5K. The first place male winner was Daniel Esposito from Columbia University. The first place female winner was Katherine Ayers from Proton Energy Systems, Inc.

Runners at the start of the Free the Science 5K run.

12

The winners of the Free the Science 5K were Katherine Ayers (left) and Daniel Esposito (right).

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

Edison Theatre ECS’s Edison Theatre offers scientists an opportunity to take their research and transform it into hands-on demonstrations. This year, Robert Masse (University of Washington) gave attendees insight into his next-generation, cloud-connected electrochemistry stations start-up in the Cloud Instruments: Democratizing Electrochemistry presentation. Juan Pablo Esquivel (Instituto Microelectrónica de Barcelona) showed guests a non-toxic portable power source that is biodegradable or even compostable in the powerPAD: Biodegradable Capillary-Based Flow Battery demonstration.

Robert Masse used the Edison Theatre for a presentation on Cloud Instruments: Democratizing Electrochemistry.

Researchers from the Instituto Microelectronica de Barcelona demonstrated a non-toxic portable power pad at the Edison Theatre. The group was among the winners of the Science for Solving Society’s Problems Challenge.

Student Poster Contest The student poster session awards were handed out by Johna Leddy, ECS Vice President, in the presence of the session organizers and judges. In the category of Electrochemical Science and Technology, first place went to Mahsa Lotfi Marchoubeh (University of Arkansas), and second place went to Leanne Mathurin (University of Arkansas). In the category of Solid State Science and Technology, first place went to Isaac Taylor (Indiana University-Purdue University-Indianapolis), and second place went to Haitham Kalil (Cleveland State University).

The student poster awards are not possible without the generous service of the session organizers and the volunteer judges.

The session organizers in San Diego were Vimal Chaitanya, Pallavi Pharkya, Venkat Subramanian, and Kalpathy Sundaram. The judges were Gautam Banerjee, David Cliffel, Marca Doeff, Cortney Kreller, Oana Leonte, Mark Overberg, Robert Petro, John Staser, Alice Suroviec, Rosanne Warren, and Hui Xu.

Winners of the Z01-General Student Poster Session, from left to right, were Mahsa Lotfi Marchoubeh (First Place, Electrochemical Science & Technology), Leanne Mathurin, (Second Place, Electrochemical Scienct & Technology), Isaac Taylor, (First Place Solid State Science and Technology), and Haitham Kalil. (Second Place, Solid State Science and Technology).

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Scenes from the Student Mixer

Monday night's student mixer, sponsored by Bio-Logic, was a sellout, attended by 201 students.

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The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

Scenes from the Technical Exhibit

Special thanks go to all the meeting sponsors and exhibitors, who showcased the tools and equipment so critical to scientific research.

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

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More Scenes from the Meeting

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The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

Future Meetings 2016

2016 PRiME 2016 Honolulu, HI October 2-7, 2016

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Hawaii Convention Center & Hilton Hawaiian Village

2017

2017

231st ECS Meeting

SOFC-XV

232nd ECS Meeting

New Orleans, LA

Hollywood, FL

National Harbor, MD

May 28-June 2, 2017

July 23-28, 2017

(greater Washington, DC area)

Hilton New Orleans Riverside

Diplomat Hotel

October 1-6, 2017 Gaylord National Resort and Conference Center

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Wikiped ia

2018 233rd ECS Meeting

AiMES 2018

Seattle, WA

Cancun, Mexico

May 13-17, 2018

September 30-October 4, 2018

Seattle Sheraton and Washington State Convention Center

Moon Palace Resort

www.electrochem.org/meetings

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CSTIC 2016 The China Semiconductor Technology International Conference (CSTIC) is one of the largest annual conferences of its kind in China with industries, companies, and people representing “the architects of the electronics revolution.” It takes place in conjunction with SEMICON, China’s exhibition of its semiconductor industry; FPD, the nation’s industry trade show that focuses on flat panel display; and LED China, the world’s largest event dedicated to the entire LED industry. This year, SEMICON China took place at Shanghai New International Expo Centre on March 15-17. The extensive events attracted over 50,000 attendees and featured more than 1,000 exhibitors in a successful effort to leverage opportunities in these related and adjacent markets. Specifically, CSTIC 2016 took place on March 13-14 and was co-sponsored by The Electrochemical Society with more than 1000 attendees.

CSTIC 2016, organized by Semiconductor Equipment and Material International (SEMI), The Electrochemical Society, and The Integrated Circuit Materials Industry Technology Innovation Alliance (ICMTIA), and technically sponsored by the IEEE Electron Devices Society, continues a well-established partnership and long-time tradition, which started in 2001.

Longtime ECS member, Fellow and volunteer Prof. Cor Claeys of imec, Belgium, served as Yue Kuo Co-Chair for CSTIC 2016 after having been the General Chair for 2014 and 2015. For the second year in a row, ECS Vice President, Dr. Yue Kuo, Dow Professor of Texas A&M University, also represented ECS at the conference.

For CSTIC 2016 the papers came from 19 major semiconductor manufacturing regions in the world, including Austria, Belgium, Brazil, Canada, China, France, Germany, Hong Kong, Italy, Japan, Korea, Malaysia, Mexico, Singapore, Sweden, Taiwan, The Netherlands, United Kingdom, and the United States.

Approximately 337 papers were selected for oral presentations and approximately 100 papers for poster presentations after careful reviews by the Cor Claeys conference organizing committee. Roughly 60% of the papers came from industry.

During the opening session of CSTIC 2016 there were three conference plenary speakers: Andrea Onetti, Executive Group Vice President and General Manager, Volume MEMS & Analog Division at STMicroelectronics, Italy; Chia-Hong Jan, Intel Fellow and Director of the System-on-Chips (SOC) Technology Integration for the Technology and Manufacturing group, Intel, USA; and Qing Chu, Vice President, Huawei Technologies, China.

The ECS Best Student Paper Award winners were: • 1st place: Alberto V. de Oliveira, University of Sao Paulo, Brazil / imec, Leuven, Belgium, “Low Frequency Noise and Fin Width Study of Si Passivated Ge pFinFETS” • 2nd place: Jie Cheng, State Key Lab. of Tribology Tsinghua University, Beijing, China, “Micro-Galvanic Corrosion of Cu/ Ru Couple Potassium Periodate (KiO4) Solution” CSTIC 2017 is scheduled to be held on March 12-13, 2017 in Shanghai.

Results of the 2016 Election of Officers and Slate of Officers for 2017

Krishnan Rajeshwar President

The ECS Tellers of Election have announced the results of the 2016 election of Society officers, with the following persons elected: President— Krishnan Rajeshwar, University of Texas at Arlington; Vice President— Christina Bock, National Research Council of Canada; and Secretary— James Fenton, University of Central Florida. The terms of Johna Leddy (Vice President), Yue Kuo (Vice President), and E. Jennings Taylor (Treasurer) were unaffected by this election.

Christina Bock Vice President

At the Board of Directors meeting in San Diego, CA on June 2, 2016, members of the Board voted to approve the slate of candidates recommended by the ECS Nominating Committee. The slate of candidates for the next election of ECS officers, to be held from January to March 2017, include: for President—Johna Leddy, and for Vice President (one to be elected) Stefan De Gendt and Andrew Hoff. Full biographies and candidate statements will appear in the winter 2016 issue of Interface.

James Fenton Secretary

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2016-2017 ECS Committees Executive Committee of the Board of Directors

Krishnan Rajeshwar, Chair.............................................................................................President, Spring 2017 Johna Leddy...............................................................................................Senior Vice President, Spring 2017 Yue Kuo.................................................................................................... Second Vice President, Spring 2018 Christina Bock..............................................................................................Third Vice President, Spring 2019 James Fenton.................................................................................................................Secretary, Spring 2020 E. Jennings Taylor ......................................................................................................... Treasurer, Spring 2018 Roque Calvo.............................................................................................................Term as Executive Director

Audit Committee

Daniel Scherson, Chair.........................................................................Immediate Past President, Spring 2017 Krishnan Rajeshwar.......................................................................................................President, Spring 2017 Johna Leddy...............................................................................................Senior Vice President, Spring 2017 E. Jennings Taylor.......................................................................................................... Treasurer, Spring 2018 Stuart Swirson...........................................................................Nonprofit Financial Professional, Spring 2019

Education Committee

Mark Orazem, Chair........................................................................................................................Spring 2017 Douglas Hansen .............................................................................................................................Spring 2017 A. Robert Hillman ...........................................................................................................................Spring 2017 James Nöel.....................................................................................................................................Spring 2018 Vimal Chaitanya..............................................................................................................................Spring 2018 Anne Co..........................................................................................................................................Spring 2019 Enn Lust..........................................................................................................................................Spring 2019 Kalpathy Sundaram.........................................................................................................................Spring 2020 Alice Suroviec.................................................................................................................................Spring 2020 James Fenton.................................................................................................................Secretary, Spring 2020 Elizabeth Podhala-Murphy .......................................... Chair, Individual Membership Committee, Spring 2017

Ethical Standards Committee

Daniel Scherson, Chair ........................................................................Immediate Past President, Spring 2017 Jan Talbot....................................................................................................................Past Officer, Spring 2017 Fernando Garzon.........................................................................................................Past Officer, Spring 2018 E. Jennings Taylor.......................................................................................................... Treasurer, Spring 2018 James Fenton.................................................................................................................Secretary, Spring 2020

Finance Committee

E. Jennings Taylor, Chair ............................................................................................... Treasurer, Spring 2018 Mark Verbrugge..............................................................................................................................Spring 2017 Robert Mantz...................................................................................................................................Spring 2017 John Turner.....................................................................................................................................Spring 2018 Jean St-Pierre.................................................................................................................................Spring 2018 Tim Gamberzky................................................................................................. Term as Chief Operating Officer James Fenton.................................................................................................................Secretary, Spring 2020

Honors and Awards Committee

Peter Fedkiw, Chair ........................................................................................................................Spring 2019 Enrico Traversa................................................................................................................................Spring 2017 Pawel Kulesza.................................................................................................................................Spring 2017 Vijay Ramani...................................................................................................................................Spring 2017 Marca Doeff....................................................................................................................................Spring 2018 Takayuki Homma.............................................................................................................................Spring 2018 Francis D’Souza..............................................................................................................................Spring 2018 Joseph Stetter.................................................................................................................................Spring 2019 Rohan Akolkar.................................................................................................................................Spring 2019 R. Bruce Weisman...........................................................................................................................Spring 2019 Vimal Chaitanya..............................................................................................................................Spring 2020 Albert Fry........................................................................................................................................Spring 2020 Jean St-Pierre.................................................................................................................................Spring 2020 Krishnan Rajeshwar.......................................................................................................President, Spring 2017

Individual Membership Committee

Elizabeth Podlaha-Murphy, Chair ...................................................................................................Spring 2017 Thomas Schmidt.............................................................................................................................Spring 2017 William Mustain..............................................................................................................................Spring 2017 Giovanni Zangari.............................................................................................................................Spring 2018 Jordi Cabana...................................................................................................................................Spring 2018 Steven Policastro............................................................................................................................Spring 2019 M. Neal Golovin..............................................................................................................................Spring 2019 Rob Sides.................................................................................... Chair, Sponsorship Committee, Spring 2019 James Fenton ................................................................................................................Secretary, Spring 2020

Nominating Committee

Daniel Scherson, Chair.........................................................................Immediate Past President, Spring 2016 Fernando Garzon.............................................................................................................................Spring 2017 Gessie Brisard.................................................................................................................................Spring 2017 Jeffrey Fergus.................................................................................................................................Spring 2017 Christina Bock..............................................................................................Third Vice President, Spring 2017

Sponsorship Committee

Rob Sides, Chair.............................................................................................................................Spring 2019 Hubert Gasteiger.............................................................................................................................Spring 2017 Fred Roozeboom.............................................................................................................................Spring 2017 Prasanth Nammalwar......................................................................................................................Spring 2017 Kohei Uosaki...................................................................................................................................Spring 2018

Iwona Rutkowska............................................................................................................................Spring 2018 Shirley Meng..................................................................................................................................Spring 2018 Marion Jones .................................................................................................................................Spring 2019 Khalil Amine...................................................................................................................................Spring 2019 Paul Fanson....................................................................................................................................Spring 2019 Elizabeth Podhala-Murphy .......................................... Chair, Individual Membership Committee, Spring 2017 E. Jennings Taylor.......................................................................................................... Treasurer, Spring 2018

Technical Affairs Committee

Johna Leddy, Chair.....................................................................................Senior Vice President, Spring 2017 Krishnan Rajeshwar.......................................................................................................President, Spring 2017 Daniel Scherson....................................................................................Immediate Past President, Spring 2017 Paul Kohl.................................................................................Second Immediate Past President, Spring 2017 Christina Bock............................................................................. Chair, Meetings Subcommittee, Spring 2017 Yue Kuo.................................................................................. Chair, Publications Subcommittee, Spring 2017 Eric Wachsman...........................Chair, Interdisciplinary Science and Technology Subcommittee, Spring 2019 Roque Calvo.............................................................................................................Term as Executive Director

Symposium Planning Advisory Board of the Technical Affairs Committee

Christina Bock, Chair....................................................................................Third Vice President, Spring 2017 Robert Kostecki ............................................................................................. Chair, Battery Division, Fall 2016 Rudolph Buchheit .................................................................................... Chair, Corrosion Division, Fall 2016 Bryan Chin .................................................................................................... Chair, Sensor Division, Fall 2016 Mark Overberg ............................................................Chair, Electronics and Photonics Division, Spring 2017 Scott Calabrese Barton............................................................Chair, Energy Technology Division, Spring 2017 Mekki Bayachou ................................... Chair, Organic and Biological Electrochemistry Division, Spring 2017 Pawel Kulesza ......................................Chair, Physical and Analytical Electrochemistry Division, Spring 2017 Elizabeth Podlaha-Murphy.............................................................Chair, Electrodeposition Division, Fall 2017 Turgut Gür......................................................................Chair, High Temperature Materials Division, Fall 2017 Madis Raukas .................................................Chair, Luminescence and Display Materials Division, Fall 2017 Yaw Obeng......................................................Chair, Dielectric Science and Technology Division, Spring 2018 Slava Rotkin ....................................................................................Chair, Nanocarbons Division, Spring 2018 Douglas Riemer..... Chair, Industrial Electrochemistry and Electrochemical Engineering Division, Spring 2018 Eric Wachsman...........................Chair, Interdisciplinary Science and Technology Subcommittee, Spring 2019

Publications Subcommittee of the Technical Affairs Committee

Yue Kuo, Chair.......................................................................................... Second Vice President, Spring 2017 Christina Bock, Vice-Chair............................................................................Third Vice President, Spring 2017 Robert Savinell.......................................................................................................EST Board Chair, 5/31/2017 Dennis Hess...................................................................................................... SSST Board Chair, 12/31/2016 Petr Vanýsek............................................................................................................ Interface Editor, 5/31/2017 Vijay Ramani............................................................................................................ Interface Editor, 5/31/2017 Jeffrey Fergus..........................................................................................ECS Transactions Editor, 12/31/2017 Thomas Moffat................................................................................................................................Spring 2017 David Cliffel....................................................................................................................................Spring 2018 D. Noel Buckley..............................................................................................................................Spring 2019 Mary Yess..............................................................................................................................Term as Publisher

Meetings Subcommittee of the Technical Affairs Committee

Christina Bock, Chair....................................................................................Third Vice President, Spring 2017 Yue Kuo, Vice-Chair.................................................................................. Second Vice President, Spring 2017 Pawel Kulesza.................................................................................................................................Spring 2017 Bor Yann Liaw.................................................................................................................................Spring 2018 Adam Weber....................................................................................................................................Spring 2019 Mary Yess..............................................................................................................................Term as Publisher

Tellers of Election

Craig Arnold, Chair ........................................................................................................................Spring 2017 James Amick...................................................................................................................................Spring 2017 Norman Goldsmith..........................................................................................................................Spring 2017 Ronald Enstrom, Alternate...............................................................................................................Spring 2017 William Ayers, Alternate..................................................................................................................Spring 2017 Elizabeth Biddinger, Alternate..........................................................................................................Spring 2017

Ways and Means Committee

James Fenton, Chair......................................................................................................Secretary, Spring 2020 Venkat Subramanian.......................................................................................................................Spring 2017 R. Bruce Weisman...........................................................................................................................Spring 2017 Gessie Brisard.................................................................................................................................Spring 2018 Michael Carter................................................................................................................................Spring 2018 Yue Kuo.................................................................................................... Second Vice President, Spring 2017 Johna Leddy...............................................................................................Senior Vice President, Spring 2017

Other Representatives

Society Historian Zoltan Nagy................................................................................................................................Spring 2017 American Association for the Advancement of Science Roque J. Calvo.....................................................................................................Term as Executive Director Chemical Heritage Foundation Yury Gogotsi............................................................................................... Heritage Councilor, Spring 2018 External Relations Representative Mark Orazem..............................................................................................................................Spring 2017 National Inventors Hall of Fame Peter Fedkiw.....................................................................Chair, Honors & Awards Committee, Spring 2019

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Division News Battery Division

Nanocarbons Division

The Battery Division would like to remind ECS members of the 25th anniversary of the birth of the commercial lithium-ion battery (LIB) in 2016. To celebrate this milestone, a number of special events are being considered for the upcoming PRiME 2016 meeting to be held October 2-7 in Honolulu, HI. In addition, special issues of Interface and the Journal of The Electrochemical Society dedicated to the LIB are planned. To ensure the success of this yearlong celebration, we are soliciting funding from interested parties. If interested in donating, please contact the Battery Division treasurer, Shirley Meng, at shirleymeng@ ucsd.edu with your details. Contributions can be large or small and you can specify the use of funds: for example, student poster awards (suggested amount $1000), symposium support (suggested amount $3000), or donations for a reception.

The Battery Division is also pleased to announce a new Postdoctoral Research Award, generously sponsored by MTI Corporation and the Jiang Family Foundation for a five-year period, with the first award to be granted in 2016. The award’s primary purpose is to recognize and support development of talent and future leaders in battery science and technology. Please visit http://www.electrochem.org/battery-divisionpostdoctoral-associate-research-award for eligibility requirements and to submit an application.

There are two winners of the Battery Division Research Award in 2016, Yang-Shao Horn of the Massachusetts Institute of Technology, USA and Nobuyuki Imanishi of Mie University, Japan. In addition, Dominique Guyomard of the University of Nantes, France was awarded the Battery Division Technology Award for 2016.

See you at the PRiME meeting in October for the big celebration!

On the evening of Tuesday, May 31, 2016, the Nanocarbons Division hosted a reception to celebrate the 25th anniversary of nanocarbons research in ECS. A crowd of more than 140 people enjoyed drinks and desserts while wearing commemorative baseball caps and listening to the recollections of Barry Miller, Karl Kadish, David Schuster, and Luis Echegoyen about the group’s early days. In the years since fullerene researchers first gathered at the fall 1991 meeting, held in Phoenix that year, to hear 22 talks, this ECS special interest group has grown to become a division of the Society covering a range of topics in carbon nanostructure science and applications. The Nanocarbons Division organized nine symposia for the San Diego meeting, with more than 380 papers presented by researchers from around the world. Also on Tuesday evening, Nanocarbons Chair Bruce Weisman announced the formation of the division’s External Advisory Council and presented two divisional awards: the Roger Taylor Travel Award to Ardemis Boghossian, and the SES Research Young Investigator Award to Jiayuan Luo.

New to the ECS Honors & Awards Program ECS Battery Division Postdoctoral Associate Research Award Sponsored by MTI Corporation and the Jiang Family Foundation Visit www.electrochem.org for more details.

Interface @ 25

Joining a cardboard image of the late Richard E. Smalley in celebrating the Nanocarbons Division’s 25th Anniversary are ECS members (left to right): Avetik Harutyunyan (Honda Research Institute, USA, Vice Chair of External Advisory Council), Slava V. Rotkin (Lehigh University, NANO Vice Chair), and Bruce Weisman (Rice University, NANO Chair).

A Lookback at “ECS Classics” Paul Kohl, Editor of Interface at the time, introduced the first edition of the ECS Classics column in the spring 1994 issue by writing, “We hope to recount some of the changes experienced by the Society in a new column.” That first column was written by Norman Hackerman, who expounded on the changeover from Transactions of The Electrochemical Society (not to be confused with ECS Transactions) to the Journal of The Electrochemical Society. The ECS Classics column has appeared in numerous issues of Interface since its inception covering a wide diversity of topics written by a who’s who of ECS luminaries. Some examples: Robert Frankenthal wrote, “H. H. Uhlig Remembered,” in the spring 1995 issue; Dennis Turner wrote, “Cracking the Seal: The Evolution of the ECS Seal Through the Years,” in the summer 1996 issue; Morris Kolodney wrote, “Sacajawea and Me,” in the winter 2000 issue; Dennis Hess wrote, “Who is Thomas Callinan,” in the summer 2003 issue; and Richard Alkire wrote, “Sherlock Swann, Norman Hackerman Jr.: Electro-organic Chemist and Master Bibliographer, 1900-1983,” in the winter 2014 issue. All classics for sure!

INTERFACE

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Free the Science: Make Your Work More Accessible, Make It OA! socie t y ne ws

Reach More Readers

Quality Publications

ECS Author Choice Open Access gives you the opportunity to make your papers freely available to any scientist (or anyone, for that matter) with an Internet connection, increasing your pool of potential readers. Papers not published as Open Access can only be read by those from a subscribing institution or those who are willing to pay a fee to access it.

Our two peer-reviewed titles are among the most highly-regarded, highly-cited, and highly-ranked in their areas. Choosing to make your paper Open Access within these journals makes no difference to the quality processes we uphold at ECS—selection criteria and peer review remain exactly the same. ECS publications have always focused on maintaining the highest standards of peer review, and we will continue to maintain these practices for all manuscript submissions.

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Free the Science, Save the World

When publishing OA the copyright remains with the author.

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The author selects one of two Creative Commons (CC) usage licenses defining how the article may be used by the general public.

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CC BY license is the most liberal allowing for unrestricted reuse of content, subject only to the requirement that the source work is appropriately attributed.

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CC BY-NC-ND license is more similar to the current usage rights under the transfer of copyright agreement: it limits use to noncommercial use (NC), and restricts others from creating derivative works(ND).

Keep Your Copyright ECS’s Open Access publishing agreement with authors does not require a transfer of copyright: the copyright remains with the author.

Authors, however, must choose what kind of license they want to grant their readers. ECS offers a choice of two Creative Commons usage licenses that authors may attach to their work (see sidebar).

Article Credits You can publish your papers as Open Access for FREE if you have an Article Credit. ECS members receive one complimentary article credit per year. Authors coming from institutions with an ECS Plus subscription qualify for unlimited article credits. For members who have already used their article credit, we offer a discounted Article Processing Charge (APC) of $200 per article (that’s 75% off our already low rate—$800).

Electrochemistry and solid state science have never been more important to global health and sustainability. Our community is making key discoveries in renewable energy, medical technology, and more. Such important discoveries need maximum discoverability.

Author Choice Open Access is a good start, but ultimately we hope to open access to our entire Digital Library without charging any publication or subscription fees. We’ve launched the Free the Science initiative to make this vision a reality.

A WORD ABOUT COPYRIGHT

Visit the publications page at www.electrochem.org to learn more!

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ECS Division Contacts High Temperature Materials

Battery Robert Kostecki, Chair Lawrence Berkeley National Laboratory r_kostecki@lbl.gov • 510.486.6002 (U.S.)

Turgut Gür, Chair Stanford University turgut@stanford.edu • 650.725.0107 (U.S.)

Christopher Johnson, Vice-Chair Marca Doeff, Secretary Shirley Meng, Treasurer Doron Aurbach, Journals Editorial Board Representative

Gregory Jackson, Sr. Vice-Chair Paul Gannon, Jr. Vice-Chair Sean Bishop, Secretary/Treasurer Raymond Gorte, Journals Editorial Board Representative

Corrosion

Industrial Electrochemistry and Electrochemical Engineering

Rudolph Buchheit, Chair Ohio State University buchheit.8@osu.edu • 614.292.6085 (U.S.)

Douglas Riemer, Chair Hutchinson Technology Inc. riemerdp@hotmail.com • 952.442.9781 (U.S.)

Sannakaisa Virtanen, Vice-Chair Masayuki Itagaki, Secretary/Treasurer Gerald Frankel, Journals Editorial Board Representative

John Staser, Vice-Chair Shrisudersan (Sudha) Jayaraman, Secretary/Treasurer John Weidner, Journals Editorial Board Representative

Dielectric Science and Technology

Luminescence and Display Materials

Yaw Obeng, Chair National Institute of Standards and Technology yaw.obeng@nist.gov

Madis Raukas, Chair Osram Sylvania madis.raukas@sylvania.com • 978.750.1506 (U.S.)

Vimal Chaitanya, Vice-Chair Gangadhara Mathad, Secretary Puroshothaman Srinivasan, Treasurer Stefan De Gendt, Journals Editorial Board Representative

Mikhail Brik, Vice-Chair/Secretary/Treasurer Kailash Mishra, Journals Editorial Board Representative

Electrodeposition Elizabeth Podlaha-Murphy, Chair Northeastern University e.podlaha-murphy@neu.edu • 617.373.3769 (U.S.) Stanko Brankovic, Vice-Chair Philippe Vereecken, Secretary Natasa Vasiljevic, Treasurer Charles Hussey, Journals Editorial Board Representative

Electronics and Photonics Mark Overberg, Chair Sandia National Laboratories meoverb@sandia.gov • 505.284.8180 (U.S.) Colm O’Dwyer, Vice-Chair Junichi Murota, 2nd Vice-Chair Soohwan Jang, Secretary Yu-Lin Wang, Treasurer Fan Ren, Journals Editorial Board Representative

Nanocarbons Slava Rotkin, Chair Lehigh University rotkin@lehigh.edu • 610.758.3931 (U.S.) Olga Boltalina, Secretary Hiroshi Imahori, Vice-Chair R. Bruce Weisman, Treasurer Francis D’Souza, Journals Editorial Board Representative

Organic and Biological Electrochemistry Mekki Bayachou, Chair Cleveland State University m.bayachou@csuohio.edu • 216.875.9716 (U.S.) Graham Cheek, Vice-Chair Diane Smith, Secretary/Treasurer Dennis Peters, Journals Editorial Board Representative

Physical and Analytical Electrochemistry Energy Technology Scott Calabrese Barton, Chair Michigan State University scb@msu.edu • 517.355.0222 (U.S.) Andy Herring, Vice-Chair Vaidyanathan Subramanian, Secretary William Mustain, Treasurer Thomas Fuller, Journals Editorial Board Representative

Pawel Kulesza, Chair University of Warsaw pkulesza@chem.uw.edu.pl • +482.282.20211 (PL) Alice Suroviec, Vice-Chair Petr Vanýsek, Secretary Robert Calhoun, Treasurer Shelley Minteer, Journals Editorial Board Representative

Sensor Bryan Chin Auburn University chinbry@auburn.edu • 334.844.3322 (U.S.) Nianqiang Wu, Vice-Chair Ajit Khosla, Secretary Jessica Koehne, Treasurer Rangachary Mukundan, Journals Editorial Board Representative 22

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

Explains the current state of the science and points the way to technological advances

ECS MEMBERS Receive a Discount!

Visit us at www.electrochem.org

Despite tremendous progress in the last two decades in the engineering and manufacturing of lithium-ion batteries, they are currently unable to meet the energy and power demands of many new and emerging devices. This book sets the stage for the development of a new generation of higher-energy density, rechargeable lithium-ion batteries by advancing battery chemistry and identifying new electrode and electrolyte materials.

The first chapter of Lithium Batteries sets the foundation for the rest of the book with a brief account of the history of lithium-ion battery development.

Next, the book covers such topics as: ● Advanced organic and ionic liquid electrolytes for battery applications ● Advanced cathode materials for lithium-ion batteries ● Metal fluorosulphates capable of doubling the energy density of lithium-ion batteries

ISBN: 978-1-118-18365-6 392 PAGES ● 2013 £93.50 | €126.30 | $145.00

● Efforts to develop lithium-air batteries ● Alternative anode rechargeable batteries such as magnesium and sodium anode systems Each of the sixteen chapters has been contributed by one or more leading experts in electrochemistry and lithium battery technology. Their contributions are based on the latest published findings as well as their own first-hand laboratory experience. Figures throughout the book help readers understand the concepts underlying the latest efforts to advance the science of batteries and develop new materials. Readers will also find a bibliography at the end of each chapter to facilitate further research into individual topics.

Lithium Batteries provides electrochemistry students and researchers with a snapshot of current efforts to improve battery performance as well as the tools needed to advance their own research efforts.

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Edited by: Bruno Scrosati, K. M. Abraham, Walter van Schalkwijk & Jusef Hassoun Order your copy today and receive a discount! Visit us at www.electrochem.org

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New Division Officers New officers for the spring 2016 – spring 2018 terms have been elected for the following Divisions.

Dielectric Science and Technology Division Chair Yaw Obeng, National Institute of Standards and Technology Vice-Chair Vimal Chaitanya, New Mexico State University Secretary Gangadhara Mathad, S/C Tech Consulting USA Treasurer Purushothaman Srinivasan, Global Foundries Inc. Awards/Travel Grants Chair Peter Mascher, McMaster University Membership Chair Uros Cvelbar, Jozef Stefan Institute Symposium Chair Mahendra Sunkara, University of Louisville Members-at-Large Sacharia Albin, Norfolk State University Gautam Banerjee, Air Products and Chemicals Inc. Daniel Bauza, IMEP William Brown, University of Arkansas Zhi Chen, University of Electronic Science and Technology of China Toyohiro Chikyow, National Institute for Materials Science Library John Flake, Louisiana State University Reenu Garg, International Rectifier Dennis Hess, Georgia Institute of Technology Michel Houssa, University of Leuven Hiroshi Iwai, Tokyo Institute of Technology Pooran Joshi, Oak Ridge National Laboratory Samares Kar, Indian Institute of Technology Kanpur Zia Karim, Aixtron, Inc. Paul Kohl, Georgia Institute of Technology Oana Leonte, Berkeley Polymer Technology Durga Misra, New Jersey Institute of Technology Hazara Rathore, IBM Corporation Research Center R. Ekwal Sah, Fraunhofer Institute for Solar Energy Systems Krishna Shenai, LoPel Corporation Kalpathy Sundaram, University of Central Florida Robin Susko John Susko Ravi Todi, Global Foundries Inc.

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Industrial Electrochemistry and Electrochemical Engineering Division Chair Douglas Riemer, Hutchinson Technology Inc. Vice-Chair John Staser, Ohio University Library Secretary/Treasurer Shrisudersan Jayaraman, Corning Inc. Members-at-Large James Fenton, University of Central Florida Trung Nguyen, University of Kansas Mark Orazem, University of Florida Robert Savinell, Case Western Reserve University E. Jennings Taylor, Faraday Technology Inc. John Weidner, University of South Carolina

Nanocarbons Division Chair Slava Rotkin, Lehigh University Vice-Chair Hiroshi Imahori, Kyoto University Secretary Olga Boltalina, Colorado State University Treasurer R. Bruce Weisman, Rice University Members-at-Large Mike Arnold, University of Wisconsin-Madison Jeff Blackburn, National Renewable Energy Laboratory Tatiana Da Ros, University of Trieste Francis D’Souza, University of North Texas Yury Gogotsi, Drexel University Dirk Guldi, Universitaet Erlangen-Nuernberg Dan Heller, Memorial Sloan Kettering Andreas Hirsch, Universitaet Erlangen-Nuernberg Karl Kadish, University of Houston Prashant Kamat, University of Notre Dame Richard Martel, Universite de Montreal Nazario Martin, Universidad Complutense de Madrid Shigeo Maruyama, University of Tokyo Roberto Paolesse, University of Rome Tor Vergata Tomas Torres, Universidad Autonoma de Madrid Ming Zheng, National Institute Standards and Technology

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websites of note

by Petr Vanýsek Physics and Mechanics There is no inherent electrochemistry of materials science in this video. While it shows mechanical movement and behavior of magnetic spheres, it is far from intuitive. It could serve as an inspiration for the MEMS/NEMS technical interest, but it will be interesting to anybody mechanically inclined.

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Andrew LaSane: Marbles fall because of gravity, until they don’t. https://www.youtube.com/watch?feature=player_embedded&v=QQ9gs-5lRKc

An Editorial in This Issue: A Followup •

Industrie 4.0 has now arrived on the global agenda! Report from the Hannover Messe http://www.hannovermesse.de/en/news/industrie-4.0-has-now-arrived-on-the-global-agenda.xhtml

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The Future of Jobs: Employment, Skills and Workforce Strategy for the Fourth Industrial Revolution http://www3.weforum.org/docs/WEF_Future_of_Jobs.pdf

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The Future of Employment. Which jobs are threatened by the onset of Industry 4.0. http://www.oxfordmartin.ox.ac.uk/downloads/academic/The_Future_of_Employment.pdf

About the Guest Author

Petr Vanýsek is a co-editor of Interface and substituted for Zoltan Nagy for this installment of “websites of note.” An emeritus professor of chemistry and biochemistry at Northern Illinois University, Prof.

Vanýsek is presently on leave of absence and visiting in the Central European Institute of Technology in Brno, Czech Republic.

Interface @ 25 A Lookback at

currents

Jan Talbot, Interface Editor at the time, introduced a new column in the winter 1996 issue in her editorial titled, INTERFACE “Staying Current.” In that editorial she wrote, “This feature will report ECS’s involvement with other societies, the activities of those societies that are of importance to our members, and on technological policy issues.” The first installment of Currents featured news of the Federation of Materials Societies. Since the column’s debut, other societies featured include the International Energy Agency (spring 1997) and the American Association for the Advancement of Science (summer 1997). In the summer 2013 issue, Adam Heller wrote a Currents article titled, “The G. S. Yuasa-Boeing 787 Li-ion Battery: Test It at a Low Temperature and Keep It Warm in Flight.” That article was written in response to a current event at the time – electrical system problems in Boeing’s 787 Dreamliner Li-ion batteries. That article was published online in advance of the print issue because of its timeliness and the need to keep “current.”

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ECS Welcomes New Staff Member Karla Cosgriff joined ECS in December 2015 as the Director of Development. She is responsible for the Free the Science initiative which combines her previous experience in fundraising and implementing sustainability projects around the world.

Karla feels that “the broad scope of the Free the Science initiative, in terms of a new research communication paradigm, the international reach of ECS, and the opportunity to help accelerate solutions to global problems in sustainability make this a really exciting opportunity.”

Karla comes to ECS after serving as Interim Executive Director of CIRENAS, a research and education center on a 5,000 acre ranch in the Nicoya Peninsula of Costa Rica. After serving on the board for three years, Karla helped transition the organization from a familyoperated enterprise to its expanded new phase of operations and

programming to model best practices and incubate ideas related to water conservation, land management, and food production.

Her commitment to education and research blossomed when she was living in The Bahamas, where she grew up and then returned to be the Director of Development for the Cape Eleuthera Foundation as well as the Managing Director for the related marine research facility, the Cape Eleuthera Institute. In this position, Karla developed education programs in sustainable development that increased revenue by 200%, providing a solid financial base for research programs including shark conservation, sustainable fisheries, bonefish and flats ecology, energy, and waste.

Karla looks forward to connecting with the ECS community about Free the Science and other ways that members and divisions can help strengthen the Society. “Free the Science is a bold undertaking and it makes ECS a true leader in scholarly publishing. But it’s also so much bigger than ECS as our community has a real opportunity to contribute to and share solutions that can make a real difference in our world. We need science more than ever now!”

Institutional Member spotlight Molecular Rebar Design

Molecular Rebar Design, LLC (MRD), based in Austin, TX, was established to develop and commercialize a breakthrough form of modified carbon nanotubes (CNT’s), called MOLECULAR REBAR®. These are the world’s first CNT’s disentangled from the usual clumping associated with industrial-scale processes. The CNT’s are individualized through a patent-protected process which significantly enhances performance for a myriad of high-value materials.

Since 2012, MRD has focused on integrating its breakthrough technology into strategic markets while continuing to innovate and develop new and improved technologies. Whether it is enabling

significant strength and longevity in rubber and plastic products, redefining performance limitations in both lead and lithium batteries, or working with global industry leading companies to explore new fields of application, MOLECULAR REBAR untangles potential and enables performance.

Along with its channel partners, MW2 Defense, Biopact, and Black Diamond Structures, MRD has built a world-class research facility to characterize performance of both lead-acid and lithium-ion batteries.

The company has 37 full-time employees, and uses 200+ channels of battery cycling capability from coin-cell to full-size industrial batteries, potentiostat with electrochemical impedance spectroscopy capabilities, scanning transmission electron microscopy, X-ray diffraction, and mercury porosimetry for electrochemical and battery performance characterization.

Institutional membership with ECS admits your organization into an elite group of scientists, academics, and professionals. It gives your organization access to the vast arrays of information, people, and breaking research that ECS has to offer. Moreover, institutional membership secures your organization’s place within an ever expanding, collaborative network of innovative thinkers, and member organizations. To accommodate the varied needs of prospective institutional member organizations, ECS offers five different levels of institutional membership.

Each level has its own distinct set of benefits and discounts. Want to learn more about ECS membership for your company, institution or organization? Visit www.electrochem.org or contact Beth Fisher, Director of Membership Services, at beth.fisher@electrochem.org.

Support ECS and learn more about membership for your company, institution, or organization by visiting www.electrochem.org or by contacting Beth Fisher, Director of Membership Services, at beth.fisher@electrochem.org.

ECS Redcat Blog The blog was established to keep members and nonmembers alike informed on the latest scientific research and innovations pertaining to electrochemistry and solid state science.

With a constant flow of information, blog visitors are able to stay on the cutting-edge of science and interface with a like-minded community.

www.electrochem.org/redcat-blog 26

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

socie t y ne ws

ECS Sponsored Meetings for 2016 In addition to the regular ECS biannual meetings and ECS Satellite Conferences, ECS, its Divisions, and Sections sponsor meetings and symposia of interest to the technical audience ECS serves. The following is a partial list of the sponsored meetings for 2016.

Please visit the ECS website for a list of all sponsored meetings.

• 67th Annual Meeting of the International Society of Electrochemistry, August 21-26, 2016 — The Hague, The Netherlands • 5th International Conference on Metal-Organic Frameworks & Open Framework Compounds (MOF 2016), September 16-19, 2016 — Long Beach, CA • 11th European Space Power Conference (ESPC 2016), October 3-7, 2016 — Thessaloniki, Greece To learn more about what an ECS sponsorship could do for your meeting, including information on publishing proceeding volumes for sponsored meetings, or to request an ECS sponsorship of your technical event, please contact ecs@electrochem.org.

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

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socie t y ne ws Interface @ 25 A Lookback at “The Chalkboard” The Chalkboard column first appeared in the summer 2004 issue of Interface.

INTERFACE Krishnan Rajeshwar, editor at the time, introduced it with these words, “This column grew out of continuing discussions within the Society for the need to infuse new talent into it; clearly, the students of today will be the active Society members of tomorrow. . . . ‘The Chalkboard’ revisits key scientific/technological concepts in an easily digestible manner.” The title of the inaugural column was, “The Glass pH Electrode,” and was written by Petr Vanýsek. Other experts who have written for this series include: Vijay Ramani, H. Russel Kunz, and James M. Fenton, “The Polymer Electrolyte Fuel Cell,” fall 2004; Gessie M. Brisard, “An Electroanalytical Approach for Investigating the Reaction Pathway of Molecules at Surfaces,” summer 2007; Eric D. Wachsman, “Solid State Ionics,” winter 2007; Uwe Happek, “Basics of Lighting: Efficacy, Color Rendering, and Color Temperature,” winter 2009; and, John L. Stickney, “Electrochemical Atomic Layer Deposition,” summer 2011. The need to infuse new talent into ECS hasn’t stopped; likewise, The Chalkboard continues to assist in that effort.

25

In the

•

The fall 2016 issue of Interface will be a special issue celebrating the 25th Anniversary of the Commercialization of Lithium-Ion Batteries.

The issue will be guest edited by Zampachi Ogumi, Robert Kostecki, Dominique Guyomard, and Minoru Inaba, and will feature the following technical articles: “Batteries and a Sustainable Modern Society,” by John B. Goodenough; “The Dawn of Lithium-Ion Batteries,”

by Yoshio Nishi; “Importance of Coulombic Efficiency Measurements in R&D Efforts to Obtain Long-Lived Li-Ion Batteries,” by J. R. Dahn, J. C. Burns, and D. A. Stevens; “The Li-Ion Battery: 25 Years of Exciting and Enriching Experiences,” by J. M. Tarascon; and, “Lithium and Lithion-Ion Batteries: Challenges and Prospects,” by Stefano Passerini and Bruno Scrosati.

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issue of

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A special section on the upcoming PRiME 2016—the international joint meeting of The Electrochemical Society (ECS), The Electrochemical Society of Japan (ECSJ), and The Korean Electrochemical Society (KECS), with the technical co-sponsorship of the Chinese Society of Electrochemistry, the Electrochemistry Division of the Royal Australian Chemical Institute, the Japan Society of Applied Physics, the Korean Physical Society Semiconductor Division, and the Semiconductor Physics Division of the Chinese Physics Society. The meeting will be held in Honolulu, HI, October 2-7, 2016.

PRiME 2016 will also feature the 6th International ECS Electrochemical Energy Summit on October 2 focused on Recent Progress in Renewable Energy Generation, Distribution, and Storage.

•

In Student News the ECS 2016 Summer Fellowships winners will be announced along with the winners of Student Awards of ECS Divisions.

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

INTERFACE

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Editor’s note: 2016 represents the 25th anniversary of Interface. One of the special features planned for this year is a series of follow-up articles that provide current perspective on the content of the original article published in Interface in the past. The first such follow up article is contributed by James Fenton of the University of Central Florida's Florida Solar Energy Center, and provides an updated context of his original article “PV, EV and Your Home at Less Than $1 a Gallon,” which was published about 18 months ago. Though the original article was published rather recently, there has been a significant change in the average price of gasoline in the intervening period which has prompted us to revisit the assumptions underlying the original article and the derivative conclusions.

Electric Vehicles Will Save the World With a Little Help from their Friends—Energy Efficiency and Renewable Energy (batteries drivers not necessarily included)

by James M. Fenton In the Interface article “PV, EV and Your Home at Less Than $1 a Gallon”1 that appeared in the spring of 2015, I wrote:

Figure 2 of that article showed the efficiency through the cost per mile of gasoline and electric vehicles as a function of the fuel price in the U.S. For that article, gasoline prices were $3.60/gal and $3.00/ gal in 2014. For most of 2015 the price was closer to $2.00/gal than $3.00/gal and on February 15, 2016, it was only $1.83/gal in the U.S. (today May 16, 2016, it is $2.35/gal). So does this cheap gasoline mean I was wrong?

Figure 1 is an updated version of the previous article’s Fig. 2, reflecting the change in gasoline prices. I also updated the fuel efficiency from 3 miles per kWh to that of the more typical value today of 3.7 miles per kWh (my own EV gives about 3.8 miles per kWh). Even at $1.75/gal, gasoline is more than twice as expensive as using U.S. residential electricity in EVs! So I was not wrong (maybe not four times as correct though).

So gasoline is still more expensive than electricity for transportation, but is electricity produced from coal and natural gas cheaper than that from renewables? Price of fossil fuels (oil2 and natural gas3) in the U.S. are at 14 year lows. The amount of electricity generated using coal in the U.S. is at its lowest level since 19704 and last year, natural gas surpassed coal as the top U.S. fuel used to produce electricity.

Even with cheap fuels, energy efficiency is even less expensive, and over the period of 2007 to 2015 U.S. energy use declined 2.4% while GDP increased 10%.5 This appears to be good for the consumer, bad for the oil and natural gas industry and really bad for the coal industry.

Despite the sharp drop in the price of natural gas, a Gas Combined Cycle Natural Gas plant (Levelized-Cost-of-Energy (LCOE), $52 – $78/MWh) is more expensive than utility-scale solar (c-Si LCOE, $47 – $57/MWh) and wind power (LCOE, $14 – $63/MWh) with the Income Tax Credit, and renewable generation remains costcompetitive without subsidies. The average cost of generating electricity from utility-scale PV has declined ~25% from one year ago.6 This was the second straight year that renewable additions to the grid exceeded that of fossil fuel additions. Fossil fuels have lost the race against renewables for electricity generation or as shown in Fig. 2, clean energy is starting to eat fossil fuels for lunch.7 But let us get back to cheap gasoline (U.S. $1.73 gallon on Feb 22, 2016) made from that cheap oil. Oil prices are likely to fall further as oil producing countries are not slowing production, as they are desperate for cash and do not want to lose their global market share.

This has contributed to an oil glut (2 million barrels a day of excess production), which first started in 2014. Oil is primarily used as a transportation fuel, while renewables are largely electricity sources that provide power. So oil does not directly compete with renewables, but could cheap gasoline cause problems for electric vehicle sales?

Last year, sales of sport utility vehicles and pickup trucks exploded in the U.S.8 Light-vehicle sales passed 17 million in 2015; the last time that happened was in 2000. To put this in context, during the poor economy of 2009 the U.S. only sold 10.4 million light-vehicles, even though gasoline cost was not high (U.S. $2.41/gal). In 2011, when gasoline cost was U.S. $3.58/gal, President Barack Obama called for a million electric cars on the road in America by 2015. So far, Americans have bought only 400,000—and with such low gas prices, are we back to Who Killed the Electric Car?9 Maybe not. While Americans are buying pickup trucks that operate on $2/gal gasoline, Europe is buying vehicles that operate on $6/gal gasoline (a decrease from the $8/gal of 2014) and though Europe’s electricity prices are about twice as high as the U.S., their $6/gal gasoline is four times more expensive as their residential electricity used in EVs! EV sales

Fig. 1. Efficiency of gasoline and electric vehicles.

Fig. 2. African proverb (see Michael Liebreich, ref. 7).

Many of the states in the United States have not had a strong renewable energy policy in place, primarily because renewable energy was thought to be too expensive and we thought only biomass could be used to make transportation fuel. We were wrong! It’s gasoline (often imported from other states or countries) and electricity produced from coal and natural gas (also, often imported) that are too expensive.

Transportation fuel can and should be electrons or hydrogen because it is cheaper!

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Fenton

(continued from previous page)

Fig. 3. Plug-in volume and % growth by region (see EV-volumes.com, ref. 10).

have doubled in Europe, more than tripled in China and contracted by 4 % in the U.S. as shown in Fig. 3.10 More than 530,000 plug-in electric vehicles were purchased globally in 2015 (Fig. 4), a 70% increase over 2014, which itself was a 50% increase over 2013.10 Solar panels are showing similar growth, 50% each year, while LED light-bulb sales are soaring by about 140% each year. Global cumulative numbers for PHEVs passed the 1 million mark in September 2015. That said, the share of the total global auto market held by electric vehicles (EVs and PHEVs) in 2015 was still only 0.6%.

So what is holding the U.S. back? For consumers, range and price are the biggest obstacles to purchasing an electric vehicle: For the last three years EV’s retailing at less than $30,000 were not able to go 100 miles on a charge—even less in cold weather. And if you want to go 300 miles on a charge, you have to pay more than double (>$60,000).

With the average price of a new IC engine car (that can go 400 miles on a single fill up) in the U.S. at $31,000, range anxiety is a major problem. In the Interface article “Home Energy Efficiency retrofits and PV Provide Fuel for Our Cars”11 that appeared in the spring of 2015, I wrote: President Obama issued the EV Everywhere Grand Challenge to the nation on March 2012 to produce plug-in electric vehicles that are as affordable for the average American family as today’s gasolinepowered vehicles by 2022. In June of 2012, David Danielson, the U.S. DOE Assistant Secretary, referred to the Challenge as a ‘Big Hairy Audacious Goal.’ Today the current cost of the battery is $325/ kWh, while the 2022 battery technology cost target is at $125/kWh. As technology advances, and battery and drivetrain costs continue to drop, plug-in electric vehicle (PEV) sales are expected to keep increasing each year, replacing demand for petroleum with demand for electricity. This additional demand for electricity can be met by widespread deployment of renewables, such as photovoltaic (PV) solar power. (Emphasis added.)

The cost of these long-range EVs is substantially dropping as Chevrolet, Tesla, and Nissan release their long range EVs over the next few years. Chevrolet (end of 2016) and Tesla (fall of 2017) say that they will deliver 200+ mile range EVs at a price less than the

average IC engine car—including tax incentives.12 2022 is today!

GM disclosed last fall that the battery pack for the Bolt, procured from the South Korean company LG Chem, will cost just $145 per kilowatt-hour (kWh). GM is expecting the price to continue to drop to $100/kWh by 2022, as shown in Fig. 5.13,14 Analysts have predicted that the upcoming Gigafactory in Reno, Nevada will reduce Tesla battery costs to below $100 per kWh.15 Salim Morsy, Bloomberg New Energy Finance (BNEF) analyst, is the author of Bloomberg’s EV report16 that focuses on the total cost of ownership of electric vehicles, including things like maintenance, gasoline costs, and—most important—the cost of batteries up to the year 2040. Figure 6 from this report shows that U.S. car buyers are willing to look at long-range EVs once the purchase price drops.

By 2030, an electric car at $22,500 would be a practical choice for almost 70 percent of car buyers (gray line).

Bloomberg’s EV report17-19 (see Fig. 7) forecast the number of worldwide electric vehicles moving from today’s ~ 1 million (0.6%) to 41 million by 2040, representing 35% of new light duty vehicle sales. The report also looked at the rise of autonomous cars and ridesharing services like Uber and Lyft, which would put more cars on the road that drive more than 20,000 miles a year, thereby increasing the return on investment on the EV. If these new services are successful, they could increase the EV market to 50% of new cars by 2040. Even if oil stayed at $20 a barrel the adoption would be 25 percent EVs. Morsy said: “Whether the end number by 2040 is 25 percent or 50 percent, it frankly doesn’t matter as much as making the binary call that there will be mass adoption.”

Fig. 5. GM says $145 kWh battery cell costs at Chevy Bolt launch (see James Ayre, ref. 14).

On Feb 25, 2016, BNEF showed a must-see 3 minute, 39 second video “The Peak Oil Myth and the Rise of the Electric Car.”18 Using a world-wide 60 percent growth of the electric vehicle market (current rate of adoption) they found that electric vehicles could displace oil demand of 2 million barrels a day as early as 2023 (Fig. 8). That would create a glut of oil equivalent to what triggered the 2014 oil crisis. Assuming a more conservative adoption rate, the world will cross the oil-crash benchmark of 2 million barrels a few years later— in 2028.

In the Interface article “PV, EV and Your Home at Less Than $1 a Gallon”1 that appeared in the spring of 2015, I wrote: PV, EVs, buildings, and the grid—If we embrace this transformation from (a) expensive fossil fuels for transportation and (b) utility only production of electricity, to that of cheaper utility and rooftop solar plants for electricity for transportation and to power our energy efficiency retrofitted buildings and homes, we will be able to manufacture the solar PV panels, energy efficiency products, batteries, and vehicles locally. If we delay, we will be trading our addiction to expensive and often imported fossil fuels to imported PV panels, and batteries, but

Fig. 4. Global plug-in vehicle sales 2013 – 2015 (see EV-volumes.com, ref. 10).

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The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

About the Author

Fig. 6. Total addressable market for vehicles with a 200-mile range (see Tom Randall, ref. 16). at least the installation jobs would not be outsourced. The question then is will nations get out in front and surf the wave created by the solar and EV tsunami or will they drown? Will electric utilities succumb to a “Utility Death Spiral”? (As more customers adopt distributed generation installed behind the customer’s utility meter, utilities’ costs to maintain and operate the grid must be spread across a smaller customer base, raising customer rates and increasing the economic incentive to cut the connection to the grid.) Or can we all work together and look at the future as an opportunity? (Emphasis added.)

Figure 9 shows the impacts of the electrification of transportation.

By 2040, electric cars will draw 1,900 terawatt-hours of electricity (the solar and energy efficiency opportunity). That is equivalent to 10 percent of electricity produced last year. This will also represent a destruction by 2040 of 13 million barrels of oil a day, or 14 to 15% of the world’s demand for oil. So we lose our oil addiction even faster than I wrote in spring 2015, though instead of the solar and EV tsunami and a “Utility Death Spiral” we may end up in an Oil Industry “Death Spiral”, drowning in oil that no one wants? “One thing is certain: Whenever the oil crash comes, it will only be the beginning. Every year that follows will bring more electric cars to the road, and less demand for oil. Someone will be left holding the barrel.”18

James M. Fenton is the Director of the University of Central Florida’s Florida Solar Energy Center (FSEC). The U.S. DOE is currently funding programs at FSEC in: “Building America” energy efficient homes, Photovoltaic Manufacturing, Hot-Humid PV testing of large-scale PV to show bankability, train-the-trainers education for solar installations, programs to decease the soft-costs of PV installation, and management of a smartgrid education consortium for power engineering students. The U.S. DOT funds the University Electrical Vehicle Transportation Center (EVTC) at FSEC. Prior to joining FSEC, Dr. Fenton spent 20 years as a Chemical Engineering Professor at the University of Connecticut. He received his PhD in Chemical Engineering from the University of Illinois in 1984 and his BS from UCLA in 1979. He was recently elected as Secretary of The Electrochemical Society and he is a Fellow of ECS and received the Research Award of the ECS’s Energy Technology Division. He may be reached at jfenton@fsec.ucf.edu. http://orcid.org/0000-0003-1996-4021 (continued on next page)

Fig. 8. Predicting the Big Crash, when increased EV sales displace 2 million barrels of oil per day—the size of the current glut (see Tom Randall, ref. 18).

© The Electrochemical Society. All rights reserved. DOI: 10.1149/2.F01162if.

Fig. 7. Global light duty vehicle and EV annual sales, 2015 – 2040 (see Michael Liebreich, ref. 19).

Fig. 9. Electrification of transportation—impacts, 2015-2040 (see Michael Liebreich, ref. 19).

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Fenton

(continued from previous page)

References 1. J. M. Fenton, “PV, EV and Your Home at Less Than $1 a Gallon,” Electrochem. Soc. Interface, 24 (1), 41 (2015).

2. C. Krauss, “Oil Prices: What’s Behind the Drop? Simple Economics,” The New York Times, April 18, 2016, http://www. nytimes.com/interactive/2016/business/energy-environment/oilprices.html?_r=0.

3. T. Puko, “Natural Gas Sinks to 14-Year Low,” The Wall Street Journal, December 14, 2015, http://www.wsj.com/articles/ natural-gas-sinks-to-lowest-level-since-2002-1450103930.

4. B. Magill, “Coal Slides to New Low As Source of Electricity,” Climate Central, January 28, 2016, http://www.climatecentral. org/news/coal-slides-new-low-source-of-electricity-19967.

5. 2016 Sustainable Energy in America Factbook, The Business Council for Sustainable Energy, http://www.bcse.org/ sustainableenergyfactbook/#.

6. “Levelized Cost of Energy Analysis 9.0,” Lazard, November 17, 2015, https://www.lazard.com/perspective/levelized-cost-ofenergy-analysis-90/.

7. M. Liebreich, “Global Trends in Clean Energy Investment,” Bloomberg New Energy Finance EMEA Summit, October 12, 2015, London, http://www.bbhub.io/bnef/sites/4/2015/10/ Liebreich_BNEF-Summit-London.pdf.

8. B. Hulac, “Cheap Gas Fires Up Big SUV Sales, Slows Electric Cars, Hybrids,” Scientific American, September 8, 2015, http:// www.scientificamerican.com/article/cheap-gas-fires-up-big-suvsales-slows-electric-cars-hybrids/.

9. C. Paine, Who Killed the Electric Car?, Papercut Films, Culver City, Calif., 2006, http://www.whokilledtheelectriccar.com/.

10. “Global Plug-In Vehicle Sales 2015,” EV-volumes.com, http:// www.ev-volumes.com/news/global-plug-in-vehicle-sales/.

11. J. M. Fenton, “Home Energy Efficiency Retrofits and PV Provide Fuel for Our Cars,” Electrochem. Soc. Interface, 24 (1), 43 (2015).

12. J. Romm, “Game Change: Tesla And GM Announce Affordable, Long-Range Electric Cars,” Climate Progress, February 11, 2016, http://thinkprogress.org/climate/2016/02/11/3748451/ tesla-gm-affordable-electric-cars/.

13. J. Cole, “GM: Chevrolet Bolt Arrives In 2016, $145/kWh Cell Cost, Volt Margin Improves $3,500,” Inside EVs, October 2015, http://insideevs.com/gm-chevrolet-bolt-for-2016-145kwh-cellcost-volt-margin-improves-3500/.

14. J. Ayre, “$145 kWh Battery Cell Costs At Chevy Bolt Launch, GM Says,” EV Obsession, October 2015, http://evobsession. com/gm-145-kwh-battery-costs-bolt-ev-launch/.

15. S. Hanley, “Analyst predicts Gigafactory will reduce Tesla battery costs below $100 per kWh,” Ecomento, September 2015, http://ecomento.com/2015/09/24/analyst-predicts-gigafactorywill-reduce-tesla-battery-costs-below-100-per-kwh/.

16. T. Randall, “Electric Fantasy: Will the Next Tesla Sell for $25,000,” Bloomberg Technology, February 9, 2016, http://www. bloomberg.com/news/articles/2016-02-09/will-the-tesla-model3-really-sell-for-25-000.

17. “Electric Vehicles to be 35% of Global New Car Sales by 2040,” Bloomberg New Energy Finance, February 25, 2016, http:// about.bnef.com/press-releases/electric-vehicles-to-be-35-ofglobal-new-car-sales-by-2040/#_ftn2.

18. T, Randall, “Here’s How Electric Cars Will Cause the Next Oil Crisis,” Bloomberg, February 25, 2016, http://www.bloomberg. com/features/2016-ev-oil-crisis/.

19. M. Liebreich, “In Search of the Miraculous,” Bloomberg New Energy Finance Summit, April 5, 2016, New York, http://www. bbhub.io/bnef/sites/4/2016/04/BNEF-Summit-Keynote-2016.pdf.

ECS Electrochemistry

KNOWLEDGE BASE One site.

Thousands of resources.

4 Over 1,000 electrochemical definitions 4 Dozens of articles by leading experts 4 Links to 1,000 of electrochemical websites 4 Over 3,000 books and proceedings volumes listed

www.knowledge.electrochem.org 32

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

t ech highligh t s On the Benefits of a Symmetric Redox Flow Battery The development of large-scale energy storage sources is necessary to make renewable energy a viable option for the future. Electrochemical energy storage systems, and in particular, redox flow batteries (RFBs) continue to garner interest as a possible approach for long-term and large-scale energy storage.

Current RFB research has focused on metal cations in varying oxidation states in aqueous electrolytes, such as the vanadium flow battery. Despite successes in this research, RFB use remains limited due to their high cost and inadequate energy efficiency and lifetime. Researchers at Cornell University have proposed to develop a “symmetric” RFB or SFRB, utilizing a single parent molecule that when oxidized can yield both positive and negative electrode half-reactions. The use of one molecule eliminates cross-contamination between tanks in the battery assembly as well as chemical and potential gradients in the discharged state, allowing for long-term storage without degradation. Simulations performed demonstrated other operational benefits during charge-discharge cycles. For use as the parent molecule, the researchers also electrochemically characterized low-cost organic molecules, substituted diaminoanthraquinone dissolved in organic electrolytes, during galvanostatic chargedischarge cycling. It was determined that the solubility of the organic material greatly impacts energy efficiency. The researchers will next examine other synthetic modifications of these molecules to increase solubility and develop a more energy efficient SFRB device.

From: J. Electrochem. Soc., 163, A338 (2016).

Formation of a Trivalent Chromium Conversion Coating on AA2024-T351 Alloy Trivalent chromium conversion coatings are an attractive alternative to chromate (i.e., hexavalent chromium) chemistries for the protection of aluminum and its alloys, as chromate is a potent carcinogen. The formation of one such commercially available trivalent chromium chemistry, formed from a bath containing zirconium hexafluoride along with trivalent chromium salts, was evaluated on AA2024-T3. This chemistry is one of several based upon a series of U.S. Navy patents from the early 2000s, and is compliant with the MIL-DTL-5541 specification. Coating formation was found to begin with activation of, and nucleation on, the cathodically active second phase particles (e.g., S, θ, and α phases) within the matrix, followed by growth on the aluminum matrix. While the initial deposition rate was comparable to that achieved on high purity aluminum, as the coating thickness increased, the alloying additions within the AA2024 began to have a significant effect, resulting in a coating approximately 50% thinner than that achieved on the high purity aluminum. The resulting coating was found

to be approximately 50 nm in thickness and to have multiple layers – an upper layer containing chromium and zirconium species over a thinner, aluminum-rich layer. A copper-enriched region was found in the alloy immediately beneath the coating. Interestingly, XPS data suggested that a small concentration of hexavalent chromium may be present in the coating.

From: J. Electrochem. Soc., 163, C25 (2016).

Modeling of Membrane Chemical Degradation in PEM Fuel Cells Polymer Electrolyte Membrane Fuel Cells (PEMFCs) have been, and remain, a technology of great interest as a power source for transportation applications and for a variety of stationary and portable applications. One of the key components of the fuel cell is the membrane, which is sometimes referred to as a proton exchange membrane (PEM) due to one of its important functions. PEMFCs are operated in low pH electrolytes and are also exposed to reactants (e.g., O2) and byproducts (e.g., H2O2) of the electrode reactions, all of which can chemically degrade the membrane, and concomitantly, the performance of the fuel cell. A 3-person research team representing two universities and three research institutions in France and Canada recently published the results of an extensive modeling investigation into chemical degradation of PEMs. The authors combined Coarse-Grained Molecular Dynamics (CGMD) with a multiscale performance model that incorporates Kinetic Monte Carlo (KMC) sub-models parameterized with Density Functional Theory (DFT) data and continuum sub-models. The authors concluded that this multi-scale, multiparadigm model can accurately simulate PEM structural changes and performance evolution, due in part to their integration of a feedback link between the performance model and the CGMD database. Degradation and performance trends predicted by the models are in good agreement with experimental data.

From: J. Electrochem. Soc., 163, F59 (2016).

Infiltration of ZnO in Mesoporous Silicon by Isothermal Zn Annealing and Oxidation Since its discovery as having efficient luminescence at room temperature, porous silicon (PS) has been explored as a promising material for optoelectronics and nanoscopic templating. PS possesses an internal surface (as high as 1000 m2/cm3) and porosity that can be varied, which embedded with an appropriate material, such as ZnO, can effect tuning of the refractive index. To date, achieving uniform ZnO infiltration has been hampered by the irregular and intricate arrangement of the pores. To overcome this difficulty, researchers from multiple institutions across the Americas and Europe investigated a two step fabrication process consisting of isothermal close space sublimation (ICSS) to infiltrate Zn in PS followed by oxidation via water

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

transported in the vapor state. Techniques such as X-ray diffraction, Rutherford backscattering spectrometry, and energy dispersive spectroscopy independently confirmed the presence of ZnO, and the likely amount of ZnO ultimately deposited. Photoluminescence spectra of various prepared samples revealed the effect and amount of ZnO present within the PS, adding green and blue bands to the red of PS. The authors concluded that the observed luminescence band can be controlled by the amount of ZnO embedded using their simple two-step process that is inexpensive and uses non-toxic precursors.

From: ECS J. Solid State Sci. Technol., 5, P6 (2016).

Laser Diode Induced Lighting Modules Phosphor-coated light emitting diodes are currently the industry standard for solid state white light emitting light sources. While they are becoming ubiquitous for consumer lighting solutions, white light LEDs can suffer from efficiency droop at high input power densities.

Another option for future lighting technology is the adoption of laser diodes (LDs), which have a negligible efficiency droop factor.

Laser diodes can be operated under high power to give high brightness in a variety of colors, depending on the output spectrum of the laser diode, and the nature of the phosphor coating. Researchers from Brunel University in London have explored the possibility of creating solid state lighting systems based on laser diodes coupled to phosphor targets, which are designed to dissipate the heat caused by high power laser sources. The team investigated the formulation of the phosphors to give a significant increase in luminous efficacy – up to 200 lm/W could be achieved.

They proposed further advances by design improvements of the lamp configuration, heat dissipation and the use of a remote phosphor configuration to allow replacement of laser diodes after failure. Laser diode approaches to solid state lighting will require continued developments to improve LD efficiency and phosphor stability, but this work demonstrates the concept of providing tailored emission for specific lighting applications using laser diode architectures.

From: ECS J. Solid State Sci. Technol. 5, R26 (2016)

Tech Highlights was prepared by David Enos, Mara Schindelholz, and Mike Kelly of Sandia National Laboratories, Colm O’Dwyer of University College Cork, Ireland, and Donald Pile of Nexeon Limited. Each article highlighted here is available free online. Go to the online version of Tech Highlights, in each issue of Interface, and click on the article summary to take you to the full-text version of the article.

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2016 PRiME 2016 = Sunday, October 2, 2016 = Honolulu, Hawaii Hawaii Convention Center & Hilton Hawaiian Village

Recent Progress in Renewable Energy Generation, Distribution, and Storage The ECS Electrochemical Energy Summit (E2S) brings together policy makers and researchers as a way of educating attendees about the critical issues of energy needs and the pivotal research in electrochemical energy that will impact our planet’s sustainability.

The 6th International ECS Electrochemical Energy Summit will focus around Recent Progress in Renewable Energy Generation, Distribution, and Storage.

The program will include keynote presentations and remarks from DOE, NEDO, KIER, and the Hawaii State Energy Office followed by a poster session showcasing research, advancements, and technologies within the clean energy sector. There will be networking opportunities and associated receptions.

Chair Boryann Liaw, Hawaii Natural Energy Institute Organizers Adam Weber, Lawrence Berkeley National Laboratory Hiroyuki Uchida, University of Yamanashi Won-Sub Yoon, Sungkyungkwan University Mark Glick, Hawaii State Energy Administrator PRiME 2016 is the joint international meeting of:

2016 Fall Meeting of The Electrochemical Society of Japan

230th Meeting of The Electrochemical Society

2016 Fall Meeting The Korean Electrochemical Society

technical co-sponsors: Chinese Society of Electrochemistry

Electrochemistry Division of the Royal Australian Chemical Institute

Korean Physical Society Semiconductor Division

The Japan Society of Applied Physics

Semiconductor Physics Division of Chinese Physics Society

Questions? Contact Christie.Knef@electrochem.org.

Visit www.prime-intl.org for updated E2S information including speakers and participating organizations.

Electrons as “Agents” and “Signals” of Change in Organic Chemistry, Biology, and Beyond

by Mekki Bayachou and James Burgess

T

his edition of Interface is dedicated to the field of organic and biological electrochemistry (OBE), a field that without doubt is rapidly expanding in scope on multiple fronts.

The traditional binary classification of work in this field into electrochemical studies and related transformations in organic chemistry on one hand, and the broader field of biological electrochemistry on the other, is probably outdated and lacks the granularity to adequately track and describe advances in many established topical areas and in emerging research fronts. Some of the areas pertaining to this field include: (1) electrochemical reactions of organic compounds on the macro-scale as in synthetic electrolysis; (2) electrochemical reactions in micro-reactors for optimized and selective electrosynthesis; (3) electrochemical reactions at the microand nano-scales as in analytical voltammetry or amperometry in confined environments; (4) reactions at modified electrodes whether by direct electron transfer or through the formation of wired reactive intermediates; (5) fundamental and applied aspects of electron transfer in chemical catalytic and electrocatalytic systems; (6) investigation of electrochemical behavior of functional organic and bioorganic systems; (7) fundamental and applied aspects of electron transfer activation of inorganic and organometallic complexes; (8) the fast growing field of bio-electrochemistry as applied to native biological systems, bio-inspired and bioengineered systems; (9) investigation of the effects of electrical potentials on biological systems and related studies of the mechanisms of electrochemical processes at the level of single biological components such as proteins or DNA, or at the level of organelles, live single cells, or collections of cells; and (10) electrochemistry in biomimetic systems, in medicine, and biomedical applications, for analysis, targeted drug delivery, biological stimulation, or a combination of these three aspects.

Certainly, the common denominator of all these areas of interest is the use of some electrical stimulus to effect change (e.g., synthesis, catalysis, stimulation, etc.) or to monitor change (e.g., analysis, sensing, etc.) in the system under consideration. In his science fiction novel Vingt Mille Lieues Sous Les Mers (Twenty Thousand Leagues Under The Sea), first published in 1869, Jules Verne was definitely ahead of his era in predicting the wonders of electricity and electrical stimuli. In the story, Captain Nemo, the antagonist of the novel, explains to Pierre Aronnax, the protagonist and narrator: Il est un agent puissant, obéissant, rapide, facile, qui se plie à tous les usages et qui règne en maître à mon bord. Tout se fait par lui. Il m’éclaire, il m’échauffe, il est l’âme de mes appareils mécaniques.

Cet agent, c’est l’électricité. (It is a powerful agent, obedient, quick, easy, it conforms to every use, and rules onboard as a master. It is the means to do everything. It gives me light, it gives me heat, it is the soul of my mechanical apparatus. This agent is electricity).

Of course, we don’t expect Jules Verne of the 1860s to foresee the transformative “power” of electricity and direct electrical stimuli in specific fields such as organic or biological chemistry, but the leap was implicit in Captain Nemo’s almost prophetic statement. Take organic synthesis as an example. Over a century of work has now proven that electrochemical methods bring unmatched benefits not only in terms of yield and selectivity in complex organic syntheses but also in terms of ease and moderate reaction conditions. Yet, outside defined circles, the use of electrochemical methods is still relatively limited in the larger synthetic community. The reluctance is akin to that of Prof. Aronnax of Jules Verne’s novel; he witnesses

the wonders of Captain Nemo’s tools and his ship Nautilus, yet he continuously challenges his capabilities and holds a strange feeling of fear and doubt of him! In this regard, the contribution by Kevin Moeller reiterates our observation that electrochemical methods in organic synthesis are, alas, still not “mainstream.” His paper sheds some light on the power of electrochemical tools in synthesis. It focuses on olefin coupling reactions, outlines the advantage of electrochemical methods, and uncovers potential or perceived hurdles. It also makes a case that, although seemingly different, the secret of carrying successful organic electrosynthesis is to work with the mindset of an organic chemist, and at times a physical organic chemist by reverting to conditions and tools (see the microarrays case) that optimally consume reactive intermediates to make the desired product while minimizing competing side reactions. In further underscoring the mindset of a physical organic chemist, Albert Fry presents computational quantum mechanical studies on the structure of organic ion-pairs formed at electrodes. The work is aimed at a better understanding of the homogeneous reactions that follow electron transfer events and the role of supporting organic electrolytes for reactions carried in organic solvents.

Besides synthesis, the capabilities of electrochemical methods also bring unparalleled insights into molecular mechanisms of complex transformations as well as governing kinetics and thermodynamics. These insights are key to understand complex reactions including catalysis, and capitalize on them to optimize processes such as transformation of organic pollutants. In this regard, Dennis Peters provides a contribution ultimately geared towards environmental dehalogenation of pollutants by catalytic reduction.

He provides a historical presentation of Nickel(I) salen catalyst, and related improvements achieved, aiming at selectively and efficiently reducing the carbon-halogen bond.

On the biological side, James Rusling contributes an article that illustrates a number of areas including electron transfer, sensing, microfluidics, and signal transduction using chemical recognition on biological systems. The article highlights the recent breakthrough of remarkable detection limits for the analysis of blood for cancer marker proteins using electrochemiluminescence readouts in a microfluidic device. A key thrust is to achieve a low cost, multiprotein panel using multiplexed immunoarray platforms for point-ofcare and clinical laboratory screening of patient serum.

While the space in this edition of Interface featuring the Organic and Biological Electrochemistry (OBE) Division does not permit us to include contributions representing all topical areas, including established and emerging fields, the list presented at the beginning of this editorial highlights important OBE research fronts that are in constant expansion and transformation. In particular, bioelectrochemistry and electrochemistry in/near live cells for the detection and monitoring of activity has opened areas of research that have brought the blurry inner workings of cells, such as the biophysics of exocytosis, to a sharper focus. Beyond single cells and collections of cells, electrochemistry at the interface of live organs such as the brain for the purpose of electrical stimulation, electrochemical detection, and targeted drug delivery represent new transformative fronts that are already opening unprecedented prospects in medicine.

Jules Verne’s description of electricity as a powerful agent that is obedient, conforms to every use, and rules as a master, also seems farsighted when we look at it as a metaphor for the current prospects

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

35

Bayachou and Burgess

(continued from previous page)

of electrochemistry in live organs such as the brain. In this regard, the farsightedness of the metaphor is further supported by the assertion of the character Pierre Aronnax, who praises Captain Nemo: Vous avez évidemment trouvé ce que les hommes trouveront sans doute un jour, la véritable puissance dynamique de l’électricité.

(Evidently, you have found what people will, without a doubt, find one day—the genuine dynamic power of electricity.)

The ever-growing “novel” of the wonders of electrochemistry in organic chemistry, biological chemistry, and now beyond (in live organs and organ systems), continues. Happy 21st century reading! © The Electrochemical Society. All rights reserved. DOI: 10.1149/2.F03162if.

About the Guest Editors Mekki Bayachou is Professor of Chemistry at Cleveland State University with Adjunct Appointment at the Pathobiology Department of the Lerner Research Institute at the Cleveland Clinic in Cleveland, OH. He earned a PhD in Chemistry from the University of Paris in France jointly with the Ecole Normale Superieure in Paris, France. He was a postdoctoral fellow at the University of California Irvine before joining Cleveland State University. Dr. Bayachou’s research has been externally funded by agencies such as the American Cancer Society, the DOE, NSF, and NIH. Dr. Bayachou’s research is in the area of functional biomaterials which is currently funded by NIH to develop biomimetic antithrombotic surfaces for bloodcontacting medical devices and implants. He also conducts research in

bioanalytical chemistry and sensor development to gain an understanding of the molecular basis of diseases. He received a number of teaching and research awards including the university-wide distinguished research award in 2007, the equivalent award in teaching in 2014, as well as recent university-wide Research Merit Recognitions in 2015 and 2016. Dr. Bayachou is currently Chair of the OBE Division of ECS. He can be reached at m.bayachou@csuohio.edu. http://orcid.org/ 0000-0002-0231-923X

James Burgess received a bachelor’s degree in chemistry from Longwood College in Farmville, Virginia, where he served as an assistant professor from 1998-2000. He earned a PhD degree in chemistry from Virginia Commonwealth University in 1997 and was a postdoctoral research associate in 1998 at Iowa State University’s Department of Energy – Ames Laboratory. He served on the faculty at Case Western Reserve University in Cleveland, Ohio, as an assistant professor and, most recently, as associate professor in the Department of Chemistry in the College of Arts and Sciences. In 2015, he has been appointed chair of the Department of Medical, Laboratory, Imaging and Radiologic Sciences in the College of Allied Health Sciences at Augusta University. Dr. Burgess oversees three nationally accredited professional programs, including Clinical Laboratory Science, Nuclear Medicine Technology and Radiation Therapy and a rapidly growing research agenda that attracts significant extramural funding. He has research interests are in the development of personalized patient diagnostics, including identifying a reliable predictor of children at risk for high cholesterol and cholesterol efflux as a diagnostic for cystic fibrosis. He may be reached at JAMBURGESS@augusta.edu. http://orcid.org/0000-0003-4128-1673

Volume 68– G l a s g o w , S c o t l a n d from the ECS Glasgow meeting, July 26-July 31, 2015 The following issues of ECS Transactions are from symposia held during the Glasgow meeting. All issues will be available in electronic (PDF) editions, which may be purchased by visiting http://ecsdl.org/ECST/. Some issues may also be available in CD-ROM editions. Please visit the ECS website for all issue pricing and ordering information. (All prices are in U.S. dollars; M = ECS member price; NM = nonmember price.)

Available Issues Vol. 68 Solid Oxide Fuel Cells XIV (SOFC-XIV) No. 1 Editors: Singhal, Eguchi

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Ordering Information To order any of these recently-published titles, please visit the ECS Digital Library, http://ecsdl.org/ECST/ Email: orders@electrochem.org

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When Ions Meet: Computational Studies on the Structure of Electrogenerated Ion Pairs

by Albert J. Fry

B

y its very nature, electrochemistry generates ions: cations at anodes and anions at cathodes. In organic electrochemistry, the initial electron transfer often initiates a series of successive steps culminating in the final product. Several of these steps typically also involve ionic intermediates. Any or all of these ions may form ion pairs with the oppositely charged ion of the supporting electrolyte. Ion pairing is almost always operative in most organic electrode reactions, even in the moderately polar solvents (acetonitrile (AN), dimethylformamide (DMF), dimethylsulfoxide (DMSO), etc.) typically employed in organic electrochemistry.1 Unfortunately there are no experimental methods, spectroscopic or otherwise, for determining the chemical structures of such ion pairs, hence, until recently, very little was known about the structures of electrogenerated ion pairs. It has become recognized in recent years that the only way to obtain structural information about ion pairs is by computational methods.2,3 The computational studies to be described here have provided for the first time the structure of ion pairs produced under electrochemical conditions.

The electrochemical reduction of polycyclic aromatic hydrocarbons (PAH’s) has been studied for many years.4,5,6 Our group,7 and Parker and Jensen8 discovered independently in 1975 that the experimental second reduction potentials (E2) of PAH’s in DMF depend upon the nature of the supporting electrolyte. E2 was observed at increasingly more negative potentials as the length of the R group was increased from ethyl through propyl to butyl. The first reduction potential (E1), on the other hand, was observed to be independent of the nature of the electrolyte; this resulted in a decrease in the spacing between the two voltammetric peaks (∆Ep) with increasing size of the R group.

Any effect that stabilizes the PAH di-anion would drive the Nernstian equilibrium for addition of an electron to the anion radical to form the di-anion to the right , thus causing E2 to appear at a less negative potential. Both groups speculated that ion pairing and/or solvation might provide such stabilization7,8 and thus cause the dependence of E2 upon the nature of the supporting electrolyte. The fact that E1 is unaffected by the electrolyte was interpreted as evidence that there is little or no ion pairing between R4N+ and the anion radical in DMF, whereas the more highly charged PAH di-anion will have a higher electrostatic attraction for the electrolyte cation and thus be much more likely to participate in ion pairing. It was suggested by the two groups that the observed shifts with increasing size of the electrolyte cation were caused by a steric effect on ion pairing to the electrogenerated di-anion. Unfortunately, although this hypothesis has been widely accepted in the literature, there was no method available at that time to test it and so the issue was not pursued further. Several years ago, recognizing that enormous advances in computers and computational methods had been made since our 1975 paper,7 I decided to reopen the issue by applying density functional theory (DFT) quantum chemical computational methods. My intention at that point was to see whether the reported voltammograms could be reproduced by DFT computations. This hope was eventually realized quite successfully,9,10 but space limitations here do not permit describing those computations.

However, in the course of that work it became clear that the computed structures of the ion pairs were quite unexpected, though chemically reasonable. This is the topic of this review.

The Tipping Effect in Tetraalkylammonium/arene Di-Anion Ion Pairs A model of a representative ion pair (that between tetrabutylammonium ion and anthracene dianion (Bu4N+/Anth-2) was constructed and DFT methods were applied to determine its structure. To do so, it was first necessary to consider the likely relative geometries of the individual components of the ion pair. Anthracene itself is a planar molecule and DFT computations indicated that the di-anion retains the planar geometry. What about the geometry of the Bu4N+ ion? The four bonds to nitrogen in ammonium (NH4+) are tetrahedrally disposed around nitrogen and so the ammonium ion is itself tetrahedral. It might seem a reasonable extrapolation from this to assume that the butyl groups in Bu4N+ are also tetrahedrally disposed around nitrogen. Considering the rotations around the various single bonds of the alkyl groups, this would give rise to a roughly spherical shape for the ion. This would explain the apparent steric effect, since the length of the chain and hence the size of the sphere would be expected to increase through the series Et < Pr < Bu. However, a fact which wasn’t known in 1975, the preferred geometry of all R4N+ ions with R = ethyl or larger is actually not tetrahedral, as many X-ray structures of such ions have shown.11 The four bonds around nitrogen are indeed tetrahedrally disposed, but the overall structure of the ions is not tetrahedral because of steric repulsions between the chains. The butyl groups actually constitute two 9-membered chains, with all carbon atoms in each chain in the anti conformation. The two chains lie in parallel planes (Fig. 1) and for this reason the structure has been referred to as quasi- or pseudo-planar.11 A view perpendicular to the pseudo-plane clearly illustrates the two chains (Fig. 2a). The ion is therefore fairly flat, as are all other tetraalkylammonium ions in which the attached groups are ethyl or larger. The next question one may ask is how the two ions fit together in the ion pair. The intuitive picture one might well have is one in which the two planar (or nearly (continued on next page)

Fig. 1. Model of tetrabutylammonium ion without hydrogen atoms, illustrating its quasi-planar structure.

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37

Fry

(continued from previous page)

(a)

(b)

Fig. 2. Model of tetrabutylammonium ion illustrating its quasi-planar geometry. (a) Left: front view (perpendicular to quasi-plane). (b) Right: side view (parallel to quasi-plane).

so) ions lie in parallel planes, with the Bu4N+ ion centered above the anthracene di-anion. However, here again intuition fails. To develop an understanding of why this is so, it’s first necessary to appreciate that while the central nitrogen atom of the cation is customarily written with a positive charge, quantum chemical computations at all levels of sophistication all agree that in tetraakylammonium ions each of the hydrogen atoms actually carries a small positive charge and all of the carbons and the central nitrogen atom carry a negative charge (Fig. 3).

Ion pairing of tetraalkylammonium ions to anions therefore arises from a reciprocal attraction between the negatively charged anion and positively charged hydrogen atoms of the cation. However, most of the hydrogen atoms will not be in a position to exert such attraction; in order to form an ion pair by electrostatic attraction a hydrogen atom must be positioned such that it is accessible to an approaching anion. If one orients the Bu4N+ ion with one chain vertical and the other horizontal (Fig. 2a), it can be seen that the horizontal chain has eight hydrogen atoms, distributed in two parallel rows of four each, positioned to interact with an anthracene di-anion approaching from the right side in Fig. 2b. The other hydrogen atoms of the horizontal and vertical chains are all either too far away or are pointed to the rear and away from the anion, and so cannot participate in ion pairing. (Of course, this chain can also form ion pairs by attack from the opposite face of the plane, but similar arguments would apply to attack on that side.) The eight hydrogen atoms can be further subdivided into an upper row of four, shown in green in Fig. 2, and a parallel lower row, shown in yellow. All eight hydrogens could in principle be directed toward the hydrocarbon anion to produce an ion pair in which the planes of both the anion and cation would be parallel in the ion pair.

However, computations show that this does not take place.10 The computed structure is highly unsymmetrical (Fig. 4). This structure is described as “tipped” because it can be viewed conceptually as though the planar anion had initially approached with its plane perpendicular to the quasi-plane of the cation, followed a clockwise rotation around the axis defined by the horizontal chain (as defined by Fig. 2b). These two motions undoubtedly take place not stepwise, but concertedly as the two species become closer. The structures of eighteen PAH dianion/tetraalkylammonium ion pairs (R4N+/Ar-2) with R ranging from ethyl through heptyl and with Ar ranging through anthracene, perylene, and chrysene, were computed.10 Every one exhibited the same tipped geometry. Why does tipping take place? Although it would probably not have been expected in advance, it is in fact very chemically reasonable. If the two components had simply approached each other in parallel planes, the eight carbon-hydrogen bonds of the cation would all be directed at angles to the plane of the anion. However, in the tipped geometry the upper row of four (green) are perpendicular to and pointed directly at the anthracene di-anion.10 Positioning four hydrogen atoms perpendicularly seems to be energetically more favorable than directing all eight hydrogens obliquely. (The hydrogen atoms in yellow are unable to participate in ion pairing because the same rotation that orients the top chain toward the di-anion rotates these away from the anion.) Another favorable feature of this geometry derives from the fact that tipping rotates another pair of hydrogen atoms of the “vertical” chain toward the di-anion, providing additional stabilization (Fig. 4).10 Thus, while tipping is surprising and certainly not intuitive, it permits the strongest attraction between the two species. To determine whether this phenomenon is unique to tetraalkylammonium-PAH dianion ion pairs, it then became necessary to examine the structure of other anions.

Nitroarene Di-Anions and Related Species

Fig. 3. Charge on individual atoms in the tetrabutylammonium ion. Color code: Green, positive; bright red, highly negative; dark red, slightly negative.

38

It has been known for many years that nitrobenzene is readily reduced to a stable anion radical.12 When the interaction of this anion and the corresponding di-anion with tetraalkylammonium (R4N+) ions was examined computationally, it turned out that ion pairing does not take place to the aromatic ring as seen with anthracene and other PAHs.9 Instead, the ion pair is formed between the cation and the nitro group, since most of the negative charge is located on its oxygen atoms (Fig. 5).12,13 Once again the hydrogen atoms of the upper horizontal chain (in green) are pointed directly at the oxygen atoms and are in the The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

Fig. 4. Ion pair between tetrabutylammonium ion/anthracene dianion. The arrow indicates the interaction of a methylene group of the vertical chain with the anthracene di-anion.

Fig. 6. Computed structure of the tetrabutylammonium/nitrosobenzene anion radical ion pair, illustrating 90° rotation of the nitrosobenzene relative to Fig. 5.

Fig. 5. Computed structure of tetrabutylammonium/nitrobenzene anion radical ion pair.

plane defined by the nitro group and the benzene ring. Thus, this ion pair exhibits the same tipped geometry as the tetraalkylammonium/ PAH ion pairs. The two oxygen atoms of the nitro group clearly participate equally in ion pairing. However, when the anion contains only one oxygen atom (nitrosobenzene and benzaldehyde anion radicals), the benzene plane is rotated 90° relative to that in Fig. 5, to bring the oxygen atom near to the β-methylene group of the upper vertical chain (Fig. 6), thus supporting the hypothesis that additional stabilization is provided by donation of that pair of hydrogen atoms to the anion.14

Ion Pairs to Inorganic Ions The computations described to this point have elucidated the structures of ion pairs between tetraalkylammonium ions (R4N+ with R ranging from ethyl through heptyl) and a wide variety range of organic structures (polycyclic aromatic hydrocarbons, nitrobenzenes, nitrosobenzenes, and substituted benzaldehydes), each bearing charges from 0 to –2. In every one of more than 100 such combinations, the tetraalkylammonium ion is in the tipped conformation. One might still have lingering doubts about the generality of this phenomenon, though, based on the fact that these anions are all planar. For this reason, the ion pairs between tetrabutylammonium ion and a series of inorganic

Fig. 7. Computed structure of the tetrabutylammonium/ phosphate ion pair.

ions were recently examined.15 Inorganic species potentially represent a more diverse ion-pairing situation because their geometries vary widely (linear, spherical, and tetrahedral). Nevertheless, in every one of these ion pairs, the tetraalkylammonium ion is tipped, exactly as with the purely organic structures previously examined. The ion pair with sulfate ion is representative (Fig. 7).15 The ion-pairing association constants increase as expected with the degree of charge on the donor species.

On the Origin of the “Steric” Effect of Electrolytes on Reduction Potential As noted earlier, the second reduction potential (E2) of polycyclic aromatic hydrocarbons were found in 1975 to shift to increasingly more negative potentials as the size of R in R4N+ increases from ethyl through propyl to butyl (and larger).7,8 Both groups made the inference that the shift in E2 with the size of R is due to increasing steric hindrance to ion pairing. But recall that these ions prefer the quasi-planar conformation.13 In this geometry, the steric hindrance

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(continued on next page) 39

Fry

Conclusions

(continued from previous page) Table I. Charges on α-methylene groups, free energies of association, and ion pairing association constants for ion pairing between tetraalkylammonium ions and nitrobenzene di-anion.

Computed property

Quantum chemical computations on more than 100 ion pairs between tetraalkylammonium ions of varying size and a wide variety of organic and inorganic ions show that in every case the ions favor the same mode of contact, suggesting this to be the first known general ion-pairing motif in organic systems. The ion pair is held together by the electrostatic attraction of a small number of hydrogen atoms of the cation for anions. The results will be of wider interest than in electrochemical contexts, e.g., studies of molecular recognition.

Recent computations on pairing involving other types of cation will be described elsewhere.

Ethyl

Propyl

Butyl

Pentyl

Hexyl

Heptyl

+0.638

+0.598

+0.576

+0.570

+0.570

+0.558

∆Gassoc, (kcal/mol)

-5.56

-5.32

-5.22

-5.29

-4.87

-4.83

© The Electrochemical Society. All rights reserved. DOI: 10.1149/2.F04162if.

Kassoc (× 10-3)

12.0

8.0

6.8

7.6

3.8

3.5

About the Author

Total Charge on the the α-methylene groups in the horizontal chain

exerted by Hept4N+ should not be significantly greater than by Et4N+.

The computed charges on the α-methylene groups of a series of tetraalkylammonium ions are given in Table I together with the free energies of association and the association constants (Kassoc) for ion pairing between these ions and nitrobenzene di-anion.13 The computed association constant (Kassoc) of the nitrobenzene di-anion with Hept4N+ is smaller by a factor of only 3.4 than with Et4N+ (Table 1), which is far too small to be a steric effect. We can understand the small yet real dependence on the electrolyte cation by examining the distribution of the computed charge and the location of the hydrogens in the horizontal chain. Electrostatic effects are inversely proportional to the square of the distance between two charged atoms, and most of the hydrogen atoms of the ion are too far from the anion to exert a significant attraction upon it. We have seen earlier the evidence7,8 that tetraalkylammonium cations seem to form ion pairs less effectively as the length of the alkyl groups increase. We also saw in the preceding section that this cannot be a steric effect. In Hept4N+ ion the additional hydrogen atoms are too far away from the anion to interact with it. So why doesn’t Hept4N+ attract anions just as easily as does Et4N+? Only the α-methylene groups (those flanking the central nitrogen atom of the cation) of the horizontal row are close enough to the negatively charged oxygen atoms of the di-anion to exert any significant attraction.16 Table I shows the results of recent computations which show that both the charges on the α-methylene groups and the association constant are greatest for ethyl and drop steadily as the chain is extended. The α-methylene groups, being nearest to the anion, almost certainly play the most important role in ion pairing by the cation, and the strength of the attraction should depend on the degree of charge they bear. As the chain becomes longer, it doesn’t exert a greater steric effect; rather, the charge on the dominant methylene groups decreases. Furthermore, a dramatic demonstration of the influence of the various α-methylene groups on ion pairing can be seen by examining the charges on each the individual methylene groups in the alkyl chain (Scheme 1); Hept4N+ ion is chosen because it illustrates best the distribution of charge along the chain. It can be seen that more than 91% of the charge on the two heptyl groups of the horizontal chain in Hept4N+ is located on the α-hydrogen atoms. The other groups bear either a small positive charge or in some cases a negative charge. From this one might perhaps conclude at this point that even though this ion contains a total of 36 hydrogen atoms, it is the four α-hydrogen atoms of the “horizontal” chain that are most responsible for ion pairing. But even this would be an overestimation; in fact, as a result of tipping, only two of the four (those marked in green in Figs. 5–7) are pointed directly at the anion. Thus, our computations lead inescapably to the conclusion that ion pairs of this type are held together almost completely by the attraction of just two hydrogen atoms of the cation for nearby anions.

Albert Fry is a native of Philadelphia, Pennsylvania. After earning a BS in chemistry from the University of Michigan and a PhD in organic chemistry from the University of Wisconsin, he spent a postdoctoral year at the California Institute of Technology with George Hammond. He then joined the chemistry faculty at Wesleyan University, where he is the E. B. Nye Professor of Chemistry. Prof. Fry is a Fellow of The Electrochemical Society and received the 2008 Manuel Baizer Award in Organic Electrochemistry from The Electrochemical Society. He may be reached at afry@wesleyan.edu. http://orcid.org/0000-0002-9093-8718

References 1. C. Reichardt and T. Welton, Solvents and Solvent Effects in Organic Chemistry, Wiley-VCH:, Weinheim (2011).

2. M. Simonetta, Int. Rev. Phys. Chem., 1, 31 (1981).

3. J. Kong, P. v. R. Schleyer, and H. S. Rzepa, J. Org. Chem., 75, 5164 (2010).

4. G. J. Hoijtink, J. v. Schooten, E. d. Boer, and W. I. Aalbersberg, Rec. Trav. Chim. des Pays-Bas, 73, 355 (1954).

5. S. Wawzonek and M. E. Runner, J. Electrochem. Soc., 102, 235 (1955).

6. M. W. Peover, Electroanal. Chem., 2, 1 (1967).

7. A. J. Fry, C. S. Hutchins, and L. L. Chung, J. Am. Chem. Soc., 97, 591 (1975).

8. B. S. Jensen and V. D. Parker, J. Am. Chem. Soc., 97, 5211 (1975).

9. A. J. Fry, Phys. Chem. Chem. Phys., 12, 14775 (2010).

10. A. J. Fry, Tetrahedron, 62, 6558 (2006).

11. R. W. Alder, P. R. Allen, K. R. Anderson, C. P. Butts, E. Khosravi, A. Martin, C. M. Maunder, A. G. Orpen, C. P. S. Pourcain, J. Chem. Soc., Perkin Trans., 2, 2083 (1998).

12. A. H. Maki and D. H. Geske, J. Chem. Phys., 33, 825 (1960).

13. A. J. Fry, J. Org. Chem., 78, 2111 (2013).

14. A. J. Fry, J. Org. Chem., 78, 5476 (2013).

15. A. J. Fry, J. Org. Chem., 80, 3758 (2015).

16. A. J. Fry, Electrochem. Commun., 35, 88 (2013).

Heptyl3N+––––CH2––––CH2––––CH2–––CH2––––CH2––––CH2––––CH3 –0.333 +0.279 +0.001 +0.021 –0.006 +0.002 –0.005 +0.012 Scheme 1. Charges on methylene groups of tetraheptylammonium ion.

40

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

Catalytic Reduction of Organic Halides

by Electrogenerated Nickel(I) Salen

by Erin T. Martin, Caitlyn M. McGuire, and Dennis G. Peters

C

atalytic reduction of halogenated organic compounds by electrogenerated nickel(I) complexes first appeared in the literature as a series of publications1-5 from the laboratory of Derek Pletcher. In this early work, a family of nickel(II) procatalysts (or catalyst precursors) was employed, which included the compound [[2,2′-[1,2-ethanediylbis(nitrilomethylidyne)]bis[phenolato]]-N,N′,O,O′]nickel(II), hereafter called nickel(II) salen (1). At a variety of cathodes (mercury, glassy carbon, platinum, and gold) and in numerous non-aqueous solvent– electrolyte media [for example, dimethylformamide containing tetran-butylammonium tetrafluoroborate (DMF–TBABF4) or acetonitrile containing tetramethylammonium perchlorate (CH3CN–TMAP)], chocolate-brown nickel(II) salen (1) undergoes a reversible, metalcentered, one-electron reduction to green nickel(I) salen (2). On the basis of density functional theory, it was established later6 that reduction of nickel(II) salen can also produce a ligand-reduced form (3) of the parent complex in which a single electron is added to the carbon atom of one imino (C=N) bond of the ligand:

Furthermore, the energy of 3 was calculated to be approximately only 2–3 kcal mol–1 higher than that of 2, meaning that both reduced states of 1 are accessible electrochemically—which becomes vitally important in later discussion.

Shown in Fig. 1 is a cyclic voltammogram, recorded at 100 mV s–1 on a glassy carbon electrode in dimethylformamide containing tetramethylammonium tetrafluoroborate (TMABF4) as the supporting electrolyte, which reveals the reversible one-electron reduction of nickel(II) salen. For the experimental conditions employed, the cathodic and anodic peak potentials (Epc and Epa) are –0.95 and –0.84 V, respectively, and the cathodic and anodic peak currrents (Ipc and Ipa) are identical. What is not seen in Fig. 1 (and what must be avoided) is that, at more negative potentials, another prominent cathodic peak is observed, due to the fact that the salen ligand itself can undergo further and irreversible degradation—which destroys the desired catalytic ability of 2.

Our goals were: (a) to overcome problems associated with direct reduction of these two compounds at mercury pool or reticulated vitreous carbon electrodes; and (b) to maximize the yield of the desired product (benzylidenecyclopentane, 6). Earlier, when these two acetylenic halides were reduced directly at a mercury pool cathode,8 more than seven different products were obtained, and 6 was obtained in a yield below 25%. Then, in a subsequent investigation of the direct reduction of 6-iodo-1-phenyl-1-hexyne at a reticulated vitreous carbon electrode,9 6 was produced in a yield no greater than 38%.

A major cause of these early disappointments was that direct reduction of the starting materials at mercury and carbon cathodes requires potentials too negative to avoid concomitant reduction of the phenyl-conjugated carbon–carbon triple bond, which leads to myriad undesired species. Moreover, use of a mercury cathode affords diorganomercury compounds in substantial yields (6–66%), depending on the cathode potential. Accordingly, when we elected to employ electrogenerated nickel(I) salen to promote the reductive cleavage of the carbon–halogen bond of each starting compound, most pitfalls of the foregoing efforts were eliminated. For the nickel(I) salen-catalyzed reductions of C6H5C≡C(CH2)4Br and C6H5C≡C(CH2)4I, we obtained the desired carbocycle (6) in respective yields of 84–95% and 84– 89%; in all cases, the only other product was 1-phenyl-1-hexyne (the presence of which reveals that the phenyl-conjugated carbon–carbon triple bond is not reducible under these experimental conditions).

Choosing a Procatalyst One of the challenges that confronts an electrochemist wishing to carry out catalytic reduction of a halogenated organic substrate is what criteria must be satisfied to choose a proper catalyst precursor (or (continued on next page)

Our First Use of Electrogenerated Nickel(I) Salen Our first published effort to employ nickel(I) salen (2), electrogenerated at a reticulated vitreous carbon cathode in dimethylformamide–tetraethylammonium perchlorate (DMF–TEAP), was as a catalyst for the reductive intramolecular cyclizations of two acetylenic halides—namely, 6-bromo-1-phenyl-1-hexyne (4) and 6-iodo-1-phenyl-1-hexyne (5):7

Fig. 1. Cyclic voltammogram recorded at a scan rate of 100 mV s–1 for reversible reduction of 2.0 mM nickel(II) salen at a freshly polished glassy carbon electrode (area = 0.071 cm2) in oxygen-free dimethylformamide containing 0.050 M tetramethylammonium tetrafluoroborate (TMABF4) at 25°C. Scan goes from ca. –0.05 to –1.45 to –0.05 V. A cadmium-saturated mercury amalgam reference electrode in contact with DMF saturated with both cadmium chloride and sodium chloride was used; this electrode has a potential of –0.76 V vs. SCE at 25°C. The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

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(continued from previous page)

with cathodic and anodic peak potentials (Epc and Epa) of –0.90 and –0.81 V, respectively. Notice that because the identity and concentration of the supporting electrolyte differ from Fig. 1, there are slight differences in the peak potentials seen in Fig. 2. For purposes of this discussion, let us take the average of these last two peak potentials as the effective standard potential for the nickel(II) salen–nickel(I) salen redox couple under the extant experimental conditions, i.e., E°Ni(II) salen,Ni(I) salen = –0.85 V (or –1.61 V vs. SCE). Although theory predicts that the difference in the peak potentials should be 59 mV for a reversible one-electron process, the intrinsic resistance of the solvent–electrolyte and the fact that the scan rate is 100 mV s–1 are together responsible for the observed peak separation of 90 mV. When an appropriate correction is made for background current, the cathodic and anodic peak currents (Ipc and Ipa) are equal. Finally, curve C shows the reduction of nickel(II) salen in the presence of 2-bromoethanol.

There are two key features of this cyclic voltammogram. First, the cathodic peak current (Ipc) is enhanced by the rapid electron-transfer reaction (within the diffusion layer surrounding the cathode) between electrogenerated nickel(I) salen and 2-bromoethanol:

Fig. 2. Cyclic voltammograms recorded with a glassy carbon electrode (area = 0.071 cm2) in oxygen-free dimethylformamide (DMF) containing 0.10 M tetra-n-butylammonium perchlorate (TBAP) at a scan rate of 100 mV s–1 at 25°C: (A) 5.0 mM 2-bromoethanol; (B) 2.0 mM nickel(II) salen; (C) 5.0 mM 2-bromoethanol and 2.0 mM nickel(II) salen. Each scan starts at 0 V and goes to a more negative switching potential before returning to 0 V. See the caption for Fig. 1 for information about the reference electrode.

As quickly as electrogenerated nickel(I) salen is consumed by this last process, the resulting nickel(II) salen next to the cathode is converted anew to nickel(I) salen which reacts catalytically with additional 2-bromoethanol remaining in or entering into the diffusion layer.

Second, the anodic peak current (Ipa) disappears completely due to rapid consumption of nickel(I) salen in the diffusion layer.

What has been overlooked from the preceding discussion is that the true thermodynamic potential for reversible reduction of the substrate (2-bromoethanol) is associated with the following process by which a transient radical–anion is initially formed:

procatalyst) for the desired process. Three requirements must be met to achieve success. First, the chosen procatalyst must undergo reversible reduction at the cathode of choice. Second, in the chosen medium (solvent–electrolyte), the reduced form of the procatalyst (which plays the role of the active catalyst) must react rapidly (at a high turnover rate) with the halogenated substrate. Third, the experimentally observed potential for direct reduction of the substrate must be more negative than the potential for reduction of the procatalyst, whereas the thermodynamic potential for reversible reduction of the substrate must be more positive than that for reduction of the procatalyst. This point is of special importance, and is aided by the fact that reductive cleavage of a carbon–halogen bond is intrinsically irreversible. On the other hand, if the potential for direct reduction of the substrate happens to be more positive than that needed to electrogenerate the active catalyst, the substrate and the procatalyst will be co-reduced— and the advantage (selectivity of the cathodic process) to be gained by catalytic reduction is lost. Over the years, it has been surprising at times to discover that even experienced electrochemists do not fully appreciate the significance of all three criteria.

With reference to Fig. 2, let us examine each of the preceding criteria by considering in more detail the example of the catalytic reduction of 2-bromoethanol by electrogenerated nickel(I) salen. Shown in this figure is a set of three cyclic voltammograms recorded with a glassy carbon electrode in dimethylformamide (DMF) containing 0.10 M tetra-n-butylammonium perchlorate (TBAP) at room temperature.

Curve A depicts the cyclic voltammogram for direct reduction of 2-bromoethanol in the absence of nickel(II) salen; the single peak, with a cathodic peak potential (Epc) of –1.71 V, can be attributed to irreversible two-electron cleavage of the carbon–bromine bond to afford a carbanion (HOCH2CH2–) and a bromide ion (Br –):

Note that this cathodic peak potential is an observed parameter that depends on the experimental conditions (such as electrode material, scan rate, solvent, and supporting electrolyte). Protonation of the carbanion by adventitious water in the solvent–electrolyte will produce ethanol (the observed product). Curve B reveals the well documented and reversible nickel(II) salen–nickel(I) salen couple

42

It is this latter electron-transfer process that ultimately provides the thermodynamic driving force for successful reaction between electrogenerated nickel(I) salen and 2-bromoethanol (or some other halogenated organic compound) in the diffusion layer. Accordingly,

Fig. 3. Cyclic voltammograms recorded with a glassy carbon electrode (area = 0.071 cm2) in oxygen-free dimethylformamide (DMF) containing 0.10 M tetraethylammonium tetrafluoroborate (TEABF4) at a scan rate of 100 mV s–1 at 25°C: (A) 1.0 mM ethyl 2-bromo-3-(3′,4′dimethoxyphenyl)-3-propargyloxy)propanoate (7); (B) 1.0 mM procatalyst or (1,4,8,11-tetraazacyclotetradecane)nickel(II) bromide; (C) 5.0 mM 7 and 1.0 mM procatalyst. Each scan begins at +0.75 V and goes to a more negative switching potential before returning to +0.75 V. See the caption for Fig. 1 for information about the reference electrode.

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

for this desired electron-transfer event to take place, the standard potential for this half-reaction must be more positive than the standard potential for the nickel(II) salen–nickel(I) salen half-reaction.

Generally speaking, to provide an adequately large driving force to ensure that electrogenerated nickel(I) salen can quantitatively convert 2-bromoethanol to its corresponding anion–radical, the “effective” standard potential for this redox couple, i.e., E°M,M ̄̇ (where, for brevity, M denotes 2-bromoethanol and M ̄̇ denotes its anion–radical) should be at least 200 mV more positive than E°Ni(II) salen,Ni(I) salen. In some cases, the true standard potential (E°M,M ̄)̇ may be calculable from first principles. On the other hand, it is possible to establish the desired standard potential experimentally by the method of homogeneous redox catalysis, as developed by Andrieux and co-workers.10–12 A recent example of the application of this strategy in the authors’ laboratory exemplifies this approach.13 Once formed, [HOCH2CH2Br] ̄̇ survives only long enough (ca. 10–14 s) for one vibration of the carbon–bromine bond to occur:

To augment the arguments presented above, it is instructive to consider another project14 in our laboratory that entailed the catalytic reduction of a bromopropargyloxy ester (7) by electrogenerated nickel(I) tetramethylcyclam (8) in dimethylformamide (DMF) containing tetraethylammonium tetrafluoroborate (TEABF4).

In this case, the procatalyst (catalyst precursor) was (1,4,8,11-tetramethyl1,4,8,11-tetraazacyclotetradecane)nickel(II) bromide; the goal of this electrocatalytic process was to obtain 2-(3′,4′-dimethoxyphenyl)-3(ethoxycarbonyl)-4-methylenetetrahydrofuran (9), which is a starting material for the chemical synthesis of isogmelinol (an antitumor agent).

Shown in Fig. 3 are three cyclic voltammograms that portray the behavior of this surprisingly complicated system. Curve A shows the direct and irreversible reduction of 7. In the first step (current spike), the carbon–bromine bond undergoes two-electron reductive cleavage, leading to a product that gives rise to the cathodic peaks (waves) seen at more negative potentials; a curious reader should consult our publication15 that provides a full explanation of this cyclic voltammogram. Curve B reveals the nicely reversible nickel(II) tetramethylcyclam–nickel(I) tetramethylcyclam redox couple: Epc = –0.125 V and Epa = –0.056 V. Curve C shows what happens when nickel(II) tetramethylcyclam (the precursor of 8) is reduced to its nickel(I) counterpart in the presence of 7; there is a substantial enhancement in the cathodic current at approximately 0 V (signifying efficient catalytic reduction of 7 by 8), whereas the absence of an anodic current is expected.

As this project evolved, the choices of substrate (7) and catalyst (8) were optimal, because the desired product (9) was obtained in yields ranging from 72–85%. On the other hand, suppose that one erroneously opted to employ electrogenerated nickel(I) salen as a catalyst for the reduction of 7. In this instance, the effort would have been frustrated by the fact that nickel(II) salen and 7 would undergo co-reduction (compare curve B in Fig. 2 with curve A in Fig 3), with the likelihood that the electrolysis would proceed slowly and that undesired products would have been obtained. Once again, it should be stressed that, if the intended catalytic process is to be accomplished properly, the thermodynamic (standard) potential for reversible one-electron reductive cleavage of the carbon–bromine bond of the substrate (7) must be more positive than the standard potential for the nickel(II) tetramethylcyclam–nickel(I) tetramethylcyclam redox couple.

Death of the Catalyst Consider a controlled-potential (bulk) electrolysis of nickel(II) salen, and suppose that the goal of this electrolysis is to generate nickel(I) salen which will act as a catalyst to promote the facile reduction of an alkyl halide (such as 1-iodooctane, C8H17I). As soon as the electrolysis is begun, one would expect that the following reactions will take place:

Overall, this set of electron-transfer events will result in the net production of an octyl radical (C8H17•), which can (a) abstract a hydrogen atom from the solvent (such as dimethylformamide or acetonitrile) to form n-octane (C8H18) or (b) undergo radical coupling to yield n-hexadecane (C16H34). In a typical electrolysis of this kind, the coulometric n value is essentially 1.00 (which substantiates the proposed intermediacy of an octyl radical) and the ratio of n-octane to n-hexadecane is close to 90:10; sometimes, a trace of 1-octene (arising from disproportionation of n-octyl radicals) can be detected.6 More importantly, as long as any 1-iodooctane remains unreduced, nickel(II) salen will be continually regenerated as a procatalyst and the color of the solution will remain chocolate-brown. Beyond the moment when all of the alkyl iodide has been consumed catalytically, the first permanent excess of nickel(I) salen will be generated. Then, if the electrolysis is continued, the solution will start to exhibit the intense green color of excess electrogenerated nickel(I) salen.

Unfortunately, the ideal scenario described at the end of the preceding paragraph does not always occur and, in many instances, the final color of the solution can be dark orange or even brown which is not at all characteristic of nickel(I) salen, but much more like that of nickel(II) salen. In their earliest publications, Pletcher and co-workers1,2 saw such unexpected color changes and attributed their observations to formation of a new nickel(II) complex that appeared not to be electroactive. In the first of these papers,1 Gosden, Healy, and Pletcher stated “… decomposition of this reduced organonickel species must lead to a complex which is electroinactive, and although the exact nature of this species was not ascertained it is probably an octahedral nickel(II) complex.” In a subsequent publication,2 Healy and Pletcher reported “[An alternate pathway] again results in the formation of a nickel(II) complex but it is not the original square planar complex but an electroinactive species.” These suggestions that nickel(II) salen undergoes change during the catalytic reduction of an alkyl halide, together with our own findings, prompted a project16 conducted in our laboratory that involved the analyses of post-electrolysis solutions with the aid of high-performance liquid chromatography (HPLC). Figure 4 reveals that reduction of nickel(II) salen in the presence of an excess of 1-iodooctane results in major transformation of the original nickel(II) salen into a trio of modified and new nickel(II) species (none of which is very active catalytically). (continued on next page)

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

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Fig. 5. Structures of nickel(II) salen (upper left), monooctylated nickel(II) salen (upper right), and dioctylated nickel(II) salen (lower left and right).

Substituents shown in red were introduced via alkylation of the imino (C=N) bonds of the salen ligand during bulk electrolyses of 1.0 mM nickel(II) salen in dimethylformamide (DMF) containing 0.10 M tetraethylammonium tetrafluoroborate (TEABF4) and in the presence of 40 mM 1-iodooctane.

Fig. 4. High-performance liquid chromatograms recorded for a 1.00 mM solution of nickel(II) salen in DMF containing 0.10 M TEABF4 recorded before (inset) and after (full scale) controlled-potential electrolyses in the presence of 40 mM 1-iodooctane. These before and after results show that the original nickel(II) salen (peak A) is substantially transformed into three new nickel(II) salen species (peaks B, C, and D), the imino (C=N) bonds of which have been octylated.

By means of a combination of several NMR techniques (COSY, NOESY, and TOCSY), these new nickel(II) complexes were identified as the monoalkylated and dialkylated forms of nickel(II) salen that are pictured in Fig. 5. These experiments revealed the important fact that using electrogenerated nickel(I) salen as a catalyst for reduction of simple alkyl monohalides suffers from alkylation of the imino (C=N) bonds of the salen ligand, which can inhibit or even block the efficacy of the catalyst.

successful than ordinary nickel(I) salen for the catalytic reductions of 1-bromo- and 1-iodooctane as well as for the reductive intramolecular cyclizations of 1-bromo- and 1-iodo-5-decyne. Thus, the presence of methyl, ethyl, and phenyl substituents on the imino (C=N) bonds of the salen ligand of the procatalyst enhances the robustness of the corresponding nickel(I) catalyst.

Are Nickel(III) Intermediates Involved?

In their pioneering papers, Pletcher and co-workers1-5 suggested that interaction between electrogenerated nickel(I) salen, [Ni(I) salen]–, and a primary alkyl halide, RX, leads to a nickel(III) intermediate, [RNi(III)X salen]–:

Then the [RNi(III)X salen]– species was proposed to undergo (a) oneelectron reduction to a nickel(II) species at the cathode

or (b) reduction by an electrogenerated nickel(I) species:

Attempts to Protect or Preserve the Integrity of the Catalyst In light of the preceding paragraphs, it was of interest to examine (a) the electrochemical behavior of already alkylated nickel(II) salen complexes and (b) whether these prealkylated nickel(II) salen species might serve as viable catalyst precursors for reduction of other alkyl halides.17 Toward these ends, three different salen ligands, as well as their corresponding nickel(II) complexes, were synthesized and characterized. Structures of these three nickel(II) species are shown in Fig. 6.

Electrochemical characteristics of each new nickel(II) complex were compared with the cyclic voltammetric behavior of nickel(II) salen itself.17 For the dimethyl and diethyl analogues of nickel(II) salen, Epc and Epa were each shifted approximately 110 to 120 mV in the negative direction in comparison with nickel(II) salen, whereas peak potentials for the diphenyl species matched those for nickel(II) salen perfectly. These experimental findings were in excellent agreement with theoretical predictions based on density functional theory. A significant finding was that the performance of dimethylated nickel(I) salen as a catalyst for reduction of 1-iodobutane was better than that of unsubstituted nickel(I) salen. In other experiments, electrogenerated dimethyl nickel(I) salen proved to be more 44

In the early 2000s, our laboratory endeavored to employ in situ electrochemical–electron paramagnetic resonance (EC–EPR) studies of the nickel(I) salen-catalyzed reduction of some n-alkyl bromides and iodides to search for the possible intermediacy of organonickel(III) intermediates, such as [RNi(III)X salen]– depicted in the preceding three reactions. Despite the fact that this species should be paramagnetic, no evidence for its existence in these systems was obtained by means of EC–EPR. This is a possible feature of these reactions that deserves more attention in the future.

Recent Applications in Environmental Electrochemistry Our use of electrogenerated nickel(I) salen as a catalyst for reduction of halogenated organic compounds has been extended recently to the remediation (dehalogenation) of several classes of environmental pollutants: (a) freons, such as 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113),18 (b) pesticides, such as 4,4′-(2,2,2-trichloroethane-1,1diyl)bis(chlorobenzene) (DDT)19 and 4,4′-(2,2,2-trichloroethane-1,1diyl)bis(methoxybenzene) (methoxychlor),20 and (c) flame retardants, such as 1,2,5,6,9,10-hexabromocyclododecane (HBCD).21 The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

Fig. 6. Structural formulas for three new alkylated nickel(II) salen complexes.

Dennis G. Peters joined the chemistry faculty at Indiana University, Bloomington, Indiana in 1962, and he has been the Herman T. Briscoe Professor of Chemistry since 1975. He earned a BS degree (cum laude) from the California Institute of Technology in 1958 and a PhD degree from Harvard University in 1962. He was elected Fellow of The Electrochemical Society in 2007; and, from The Electrochemical Society, he received the Henry B. Linford Award for Distinguished Teaching in 2002 and the Manuel M. Baizer Award in Organic Electrochemistry in 2012. He has served as Secretary– Treasurer (1999–2001), Vice Chairman (2001–2003), and Chairman (2003–2005 and 2011–2012) of the Organic and Biological Electrochemistry Division of The Electrochemical Society. He can be reached at peters@indiana.edu.

References

Recent years have seen a variety of strategies for the remediation of halogenated organic pollutants. Although biological,22 chemical,23 and thermal24 processes have all been employed for this purpose, each approach has its drawbacks. Degradation through the use of microbes is often slow, and incomplete dehalogenation can occur.

Remediation via chemical means can involve the use of large volumes of harsh (and even toxic) solvents, whereas thermal decomposition (incineration) requires consumption of much energy, along with production of secondary wastes such as carbon dioxide and hydrohalic acids. There are reasons to believe that electrochemical remediation of environmental pollutants can be accomplished with lower energy consumption and with fewer objectionable products. Probably the biggest future challenge is the need for designing and constructing efficient electrochemical cells that can accommodate huge amounts of environmental pollutants. © The Electrochemical Society. All rights reserved. DOI: 10.1149/2.F05162if.

About the Authors Erin T. Martin earned a BS degree in chemistry at University of Missouri-St. Louis in 2013 and is pursuing a PhD in analytical chemistry at Indiana University, where she serves as an officer for Indiana’s Student Chapter of The Electrochemical Society. Her research at Indiana University, supervised by Professor Dennis G. Peters, is focused on the application of electrochemical reduction for the detection, degradation, and understanding of environmental pollutants at different cathode surfaces. She can be reached at etmartin@indiana.edu.

Caitlyn M. McGuire earned a BS degree in chemistry at Truman State University in 2012, and is pursuing a PhD in analytical chemistry at Indiana University under the guidance of Professor Dennis G. Peters. She presently serves as President for Indiana’s Student Chapter of The Electrochemical Society. Her research applies electrochemical reduction of organochlorine pollutants towards environmental remediation. She can be contacted at cmmcguir@ indiana.edu or caitlynmcguire@gmail.com.

1. C. Gosden, K. P. Healy, and D. Pletcher, J. Chem. Soc., Dalton Trans., 972 (1978).

2. K. P. Healy and D. Pletcher, J. Organomet. Chem., 161, 109 (1978).

3. C. Gosden and D. Pletcher, J. Organomet. Chem., 186, 401 (1980).

4. J. Y. Becker, J. B. Kerr, D. Pletcher, and R. Rosas, J. Electroanal.

Chem., 117, 87 (1981).

5. C. Gosden, J. B. Kerr, D. Pletcher, and R. Rosas, J. Electroanal.

Chem., 117, 101 (1981).

6. P. W. Raess, M. S. Mubarak, M. A. Ischay, M. P. Foley, T. B. Jennermann, K. Raghavachari, and D. G. Peters, J. Electroanal.

Chem., 603, 124 (2007).

7. M. S. Mubarak and D. G. Peters, J. Electroanal. Chem., 332, 127 (1992).

8. B. C. Willett, W. M. Moore, A. Salajegheh, and D. G. Peters, J. Am. Chem. Soc., 101, 1162 (1979).

9. M. S. Mubarak, D. D. Nguyen, and D. G. Peters, J. Org. Chem., 55, 2648 (1990).

10. C. P. Andrieux, C. Blocman, J. M. Dumas-Bouchiat, and J. M. Savéant, J. Am. Chem. Soc., 101, 3431 (1979).

11. C. P. Andrieux, C. Blocman, J. M. Dumas-Bouchiat, F. M’Halla, and J. M. Savéant, J. Electroanal. Chem., 113, 19 (1980).

12. C. P. Andrieux, C. Blocman, J. M. Dumas-Bouchiat, F. M’Halla, and J. M. Savéant, J. Am. Chem. Soc., 102, 3806 (1980).

13. J. H. Rheinhardt, M. S. Mubarak, M. P. Foley, and D. G. Peters, J. Electroanal. Chem., 654, 44 (2011).

14. A. P. Esteves, D. M. Goken, L. J. Klein, M. A. Lemos, M. J. Medeiros, and D. G. Peters, J. Org. Chem., 68, 1024 (2003).

15. A. P. Esteves, D. M. Goken, L. J. Klein, M. J. Medeiros, and D. G. Peters, J. Electroanal. Chem., 560, 161 (2003).

16. D. M. Goken, M. A. Ischay, D. G. Peters, J. W. Tomaszewski, J. A. Karty, J. P. Reilly, and M. S. Mubarak, J. Electrochem. Soc., 153, E71 (2006).

17. M. P. Foley, P. Du, K. J. Griffith, J. A. Karty, M. S. Mubarak, K. Raghavachari, and D. G. Peters, J. Electroanal. Chem., 647, 194 (2010).

18. E. R. Wagoner, J. L. Hayes, J. A. Karty, and D. G. Peters, J. Electroanal. Chem., 676, 6 (2012).

19. E. R. Wagoner, J. A. Karty, and D. G. Peters, J. Electroanal. Chem., 706, 55 (2013).

20. C. M. McGuire, A. M. Hansen, J. A. Karty, and D. G. Peters, J. Electroanal. Chem., 772, 66 (2016).

21. E. R. Wagoner, C. P. Baumberger, B. H. R. Gerroll, and D. G. Peters, Electrochim. Acta, 132, 545 (2014).

22. T. P. Baczynski, D. Pleissner, and T. Grotenhuis, Chemosphere, 78, 22 (2010).

23. S. Chiron, A. Fernandez-Alba, A. Rodriguez, and E. Garcia-Calvo, Wat. Res., 34, 366 (2000).

24. D. Bartz, R. M. Kendall, and F. E. Moreno, U.S. Patent 5,510,093, April 23, 1996.

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Low-Cost Microfluidic Arrays for Protein-Based Cancer Diagnostics Using ECL Detection

by James F. Rusling

T

he new era of Precision Medicine is expected to incorporate data on biomarker proteins in blood along with genomic data on patients and their cancers.1 A great deal of interest has been generated in biomarker protein panels for cancer diagnostics.2 Blood levels of certain proteins are biomarkers that can facilitate early cancer detection as well as individualized therapy monitoring. Measurements on protein panels are important to obtain high diagnostic power.3 These approaches promise earlier detection of cancer than possible with current tumor detection approaches and are valuable for therapy management, resulting in improved patient outcomes and decreased mortality. Unfortunately, multiple protein detection has yet to be broadly realized in clinical or point-of-care (POC) diagnostics due to the lack of low cost, sensitive, easy to use devices to measure multiple biomarker proteins in patient serum. There is also a lack of fully validated cancer biomarker protein panels for diagnostics. Time-honored measurement approaches such as Enzyme-Linked Immunosorbent Assays (ELISA) have limitations in sensitivity, analysis time, cost, multiplexing, and sample size.

Newer commercial approaches are useful for research, but rely on complex technology that may be too difficult and expensive for the clinic. Most commercial kits cannot achieve sub-pg mL˗1 detection, but some biomarker proteins have blood levels at or below this range.

In the context of current research in protein measurements, this paper describes several recent examples from our own laboratory that illustrate a move toward low cost, automated, multiplexed electrochemical immunoarrays using very simple approaches that avoid photo-lithography.4 Rather simple ideas from nanotechnology and materials science have provided new opportunities to design and fabricate such devices. Approaches include soft-polymer template molding, precision cutting of polymer sheets, and nano- and microwell printing. We rely on modern device and materials engineering as much as electrochemistry to achieve low cost, functional immunoarrays.

In addition, detection by electrochemiluminescence (ECL) is very suitable for this task since it is sensitive, easy to generate and measure, and does not require individually electrically-addressable sensor arrays.4 Arrays can be created by patterning a conductive chip with spatially-separated microwells, which is essentially just a single working electrode in a specially designed symmetric electrochemical cell. We describe such a system below which is fully automated for multiplexed protein measurements using ECL for detection.

More recently, we have explored 3D printing to produce very cheap, but sensitive multiplexed protein immunoarrays. Desktop 3D printing present new opportunities for low cost bioanalytical device fabrication by enabling fast computer-based design prototyping and testing. The devices are printed directly, avoiding the necessity for masks or templates used in more conventional approaches.5 Recent reviews summarize biological and diagnostic applications.6,7 An example of our initial efforts to fabricate 3D-printed immunoarrays is included below.

detection limits of 1-10 pg/mL for many proteins, but a new optical technology called Simoa claims sensitivity in the low fg mL˗1 range.9 However, many of these systems have cost and complexity issues that limit clinical point-of-care (POC) applications, that is measurements that can be done directly in a clinic or a physician’s office.

Recent advances in nanomaterials-enhanced microfluidic electrochemical devices have enabled multiplexed detection of proteins at levels in the low fg/mL range,3,10-14 thus covering the lower ranges of a majority of proteins in human serum. One example includes a highly nanostructured gold sensor chip.15 This chip was equipped with solution circuits for multiplexed measurements of pathogenic bacteria and antibiotic-resistance biomarkers.16 In general, nanostructured sensors coupled with massively labeled detection particles can provide very large signal enhancements.4 Screen and ink-jet printed electrode arrays are quite useful for multiplexing, can be fabricated as or converted to nanostructured sensors, and can be integrated with microfluidics to detect panels of proteins.4,17-22 Our own approach for amperometric detection of multiple proteins in microfluidic devices (Fig. 1) features an 8-sensor gold nanostructured array interfaced with a microfluidic system with capture and detection chamber.23 Magnetic bead detection particles labeled with thousands of antibodies and up to 0.5 million enzyme labels can be used. Sensitivity and detection limit can be tailored to the analytical problem at hand by adjusting numbers of enzyme labels and bead size. We applied this array approach for predictive diagnosis of oral mucositis,23 a serious complication of cancer therapy. Assay time was decreased to 8 min by trading off sensitivity while still measuring protein levels that are clinically significant.24 (continued on next page)

Clinical Protein Detection First, we discuss the state-of-the-art in multi-protein detection for medical diagnostics. While mass spectrometry is a very powerful approach for proteomics, current technology is too expensive and technically demanding for most clinical applications, and in some cases lacks the required sensitivity. Magnetic bead-based devices using optical or ECL detection hold great promise for high throughput and multiplexing.3,8 Most current commercial bead-based methods have

Fig. 1. Strategy for on-line capture of proteins by massively labeled magnetic beads with attached antibodies in microfluidic capture chamber, followed by transport to the detection chamber and electrochemical detection by injection of H2O2 to activate the enzyme label and hydroquinone mediator. Events are illustrated for one sensor in the array.

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(continued from previous page)

A panel of 4 prostate cancer biomarkers in serum was measured with detection limits of 10-100 fg/mL using this automated device.26 All the operator needs to do is load the cassette with reagents and samples, and start the microprocessor program. At the end of the assay, the operator measures the ECL output using the camera while applying 0.9 V vs SCE with a potentiostat. Typical data output is shown in Fig. 3C-G. Images recorded by the CCD camera are false-colored and converted to relative ECL intensities for sample analysis. While systems of this sort have possible commercial value, it is mainly a prototype at this point. Engineering issues associated with fabricating

(a)

Fig. 2. Strategy for ECL protein detection in a microfluidic array. The array is a microwell-patterned pyrolytic graphite chip equipped with counter and reference electrodes. Single-wall carbon nanotube forests are grown in the wells, then capture antibodies are attached to their carboxylated ends. A pump delivers sample to the array, and proteins are captured on specific spots by the antibodies. Then 100 nm RuBPY-silica nanoparticles coated with another set of antibodies are delivered and bind to proteins on the spots.

Finally, TprA solution is delivered, and a potential of 0.9-1.1 V vs. SCE is applied to generate ECL light, which is measured by a CCD camera.

An ECL Array with Automated Reagent Delivery In addition to high sensitivity, selectivity, and multiplexity already achieved in some bioanalytical systems, routine POC protein diagnostics will require full automation at a low cost per assay. This is more straightforward with ECL than with other electrochemical detection methods because ECL does not require individually addressable sensor electrodes, thus simplifying immunoarray design and electrical components.

In a widely used format for biosensors, a complex high energy redox process involving Ru(bpy)32+ dye (RuBPY) and co-reactant tripropylamine (TprA) is driven electrochemically to emit ECL light.13,15 A charge-coupled device (CCD) camera or photomultiplier tube (PMT) can easily measure this visible light (610 nm). ECL detection has been adapted in microfluidic immunoarrays to detect proteins utilizing silica beads with containing Ru(bpy)32+ dye and coated with antibodies for detection.4,22 The process used in our laboratory is shown in Fig. 2.

We designed an automated reagent and sample delivery module in an ECL-based microfluidic system for detection of proteins. This immunoarray has six microfluidic channels connected to a 6-channel detection chamber that houses a 30-well pyrolytic graphite (PG)SWCNT chip (Fig. 3) with a light-transparent top.25 The well pattern is computer generated and laser-jet printed onto glossy paper, then heat transferred onto the PG chip. The computer ink pattern is hydrophobic enough so that it encloses the hydrophilic carbon wells and prevents aqueous solution run-over and cross-contamination during SWCNT growth and antibody attachment. Detection is facilitated by the 100 nm RuBPY silica nanoparticles that are coated with antibodies to provide amplification and low fg/mL detection levels using a CCD camera. The entire device was assembled for ~$500, excluding the CCD camera and potentiostat. One micropump is connected per channel to a portable sample/reagent cassette preloaded with air-separated samples, buffers and RuBPY-silica nanoparticles. This cassette also has 6 channels, one for each detection channel. The required solutions are pumped into the 6-channel detection chamber with SWCNT wells containing capture antibody according to a preset program. Assay events are controlled by an Arduino microprocessor and open-source software to fully automate flow, reagent delivery, and incubation times.

48

(b)

(c)

(e)

(g)

(d)

(f)

(h)

Fig. 3. Automated (a) Microprocessor-controlled automated microfluidic immunoarray featuring 30 microwell SWCNT modified detection array fed with sample/immunoreagents from a reagent cassette (red) using inexpensive micropumps. The entire assay takes 36 min. Immunoassay steps (b) are automated and controlled by a microprocessor. c-d shows ECL immunoassay results for four cancer biomarkers, viz. IL-6, PF4, PSMA, PSA, at specific analyte concentrations. e-h are immunoassay calibration curves for IL-6, PF4, PSA, and PSMA. Adapted from ref. 25 with permission, Copyright 2015.

American Chemical Society.

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

and housing components into a single integrated automated device with on-board measurement electronics and diagnostic output delivery to the physician still need to be addressed for POC use.

A 3D-Printed Immunoarray Desktop 3D printers promise large cost savings for optimized bioanalytical device fabrication with little compromise in sensitivity, selectivity or reliability. These advantages, when integrated with full automation, could help push protein-based cancer diagnostics into POC clinical use. Our first effort in this direction resulted in a prototype protein immunoarray fabricated by using a desktop Fused Deposition Modeling (FDM) 3D printer, the MakerBot Replicator 2X. This new immunoarray was printed from polylactic acid (PLA) (Fig. 1) and features an open channel housing a screen-printed carbon 4-sensor array. The immunoarray is powered by a supercapacitor for ECL generation, thus avoiding the potentiostat, but still uses CCD camera detection.26 The supercapacitor is recharged after each assay measurement with a light activated solar cell. The device utilizes three 170 µL reagent reservoirs with plugging cap inserts that seal them to stop the flow (Fig. 4A, on right). These reservoirs are connected to a downstream microfluidic channel housing the 4-sensor array (Fig. 4). Initially, the insert caps seal the reservoirs and no solution flows. When a cap is removed, solution in that reservoir flows into and completely fills the 160 µL sensor channel by gravity flow. To run the assay, the reagents are released in the proper sequence by removing the insert caps.

A movable, lever-controlled platform holds the sensor array, reagent reservoirs and a larger removable wash reservoir. A waste reservoir is positioned underneath the sensors (Fig. 4B). Wash reservoirs employ similar plugging inserts as reagent reservoirs to control flow.

Removing the insert and changing the lever to wash position tilts the sensor array 25º to wash surplus reagents to waste.

The sensors in the array have antibodies attached to capture the analytes proteins. Assays begin by opening the sample reservoir to fill the detection chamber, allowing incubation for antibodies to capture the analyte, then sequential washing. Then, RuBPY-silica-antibody detection nanoparticles are added from their reservoir, followed by washing, and an incubation period. Now, RuBPY-silica-antibody particles have bound onto analyte proteins on the sensors to complete the immunoassay binding steps. For detection, TPrA co-reactant is released from its reservoir to fill the detection channel and the supercapacitor is discharged for 30 s to supply 1.2 V. This generated ECL light from RuBPY in the nanoparticles, with light measured by the CCD camera. Assays took 35 min, after which the supercapacitor

(a)

was recharged with small solar panel and light from a cell phone or the sun for the next assay. In this approach, the CCD camera is the only expensive reusable hardware required.

Detection of prostate cancer biomarker proteins prostate specific antigen (PSA), prostate specific membrane antigen (PSMA) and platelet factor-4 (PF-4) in serum was done with this immunoarray.27 Detection limits of 0.3-0.5 pg mL˗1 were achieved for these 3 proteins in serum. While calibration curves show a small upward curve, they are suitable for protein detection over six orders of magnitude of serum concentration (Fig. 5). Analysis of prostate cancer patient serum samples gave good correlation with standard ELISA. This 3D-printed, portable immunoarray device costs ~$1.00 in materials with single-use electrode array ($0.20) provides 3-protein assays for $0.50 each in reagents. Power is supplied by a reusable Cellergy, 2.1 V, 80 mF supercapacitor at $10) with a Sparkfun solar panel ($12) for recharging. Manual operation is a limitation for pointof-care (POC) use. However, this successful prototype suggests that low cost, workable automated immunoarray devices can be easily designed and 3D-printed in the future.

A limitation of the above system is the open detection chamber, which we used because FDM printers produce opaque devices.

However, the Form1+ 3D printer (Formlabs) can use clear methacrylate-based resin, and can be polished using abrasive papers, rinsed, then spray-coated with clear acrylic (Krylon, Cleveland, OH) to achieve 90% transmission of visible light.27 This approach is amenable to biosensor designs using ECL detection.

Summary and Future Outlook Current practice in diagnosing cancer relies mainly on biopsies, identifying patient symptoms or lesions, and in vivo imaging. These approaches often require locating a tumor, making detection difficult and compromising therapy outcomes when detection occurs at advanced stages. If biomarkers are used at all, tests are often limited to only one or two proteins. Screening for early stage cancers without detecting tumors can be achieved from assays of blood for cancer biomarker proteins to provide an instantaneous snapshot of disease status.2,3 Devices to measure biomarker proteins should be accurate, sensitive, cheap and preferably point-of-care (POC).

As discussed above, recent research has shown that high sensitivity and good accuracy is possible to achieve using ECL and other detection approaches. However, low cost, assay simplification, and (continued on next page)

(b)

Fig. 4. 3D-printed gravity-fed microfluidic array and wash reservoir module. (A) Basic array showing three reagent reservoirs at top equipped with inserts along with flow path for reagents to reach detection channel. (B) Wash reservoir module (1B Left) 3D model showing freely moving lever to change between wash and load position along with wash reservoirs aligned with main array, (1B Right) assembled immunoarray with both main array and wash module. Reprinted with permission from Ref. 26. Copyright Elsevier 2016.

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(continued from previous page)

(a)

(b)

(c)

(d)

Fig. 5. Calibration data from the 3D printed gravity-fed immunoarray for 3 proteins in undiluted calf serum showing influence of biomarker protein concentration on ECL response: (A) Recolorized ECL images of 8 arrays with showing increase in ECL intensity with increased concentration. ECL signals digitized for (B) PSA, (C) PSMA and (D) PF-4 in calf serum. Error bars show standard deviation for n = 4. Reprinted with permission from Ref. 26. Copyright Elsevier 2016.

full automation are just beginning to be addressed in the context of POC devices. We believe that 3D printing can contribute significantly to these goals for the future and perhaps eventually to very cheap, automated detection of a wide variety of biomarker proteins. © The Electrochemical Society. All rights reserved. DOI: 10.1149/2.F06162if.

Acknowledgements Preparation of this article and the author’s work described herein was supported financially by grant No. EB016707 from the National Institute of Biomedical Imaging and Bioengineering (NIBIB), NIH. The author is grateful to collaborators and research students cited herein without whom progress in this area would not be possible.

50

About the Author James F. Rusling was awarded the BSc in chemistry from Drexel University in 1969, and PhD from Clarkson University in 1979. He is professor of chemistry at University of Connecticut, professor of surgery and member of the Neag Cancer Center at University of Connecticut Health Center, and adjunct professor of chemistry at National Univ. of Ireland, Galway.

Current research includes new cancer diagnostic via detection of biomarker proteins, electrochemical and mass spectrometric arrays for toxicity screening, tumor suppressor gene damage, and fundamental bioelectrochemistry.

He has authored over 350 research papers and several books, and is a musician interested in Irish and American folk styles. He may be reached at james.rusling@uconn.edu.

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

References 1. I. S. Kohane, Science, 349, 37 (2015).

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Oncol., 8, 142 (2011).

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4. J. F. Rusling, G. W. Bishop, N. Doan, and F. Papadimitrakopoulos, J. Mater. Chem. B, 2, 12 (2014).

5. B. C. Gross, J. L. Erkal, S. Y. Lockwood, C. Chen, and D. M. Spence, Anal. Chem., 86, 3240 (2014).

6. C. Meng, B. Ho, S. Huan Ng, K. Ho, H. Lia and Y.-J. Yoon, 3D printed microfluidics for biological applications, Lab on a Chip, 15, 3627 (2015).w 7. P. F. O’Neill, A. Ben Azouz, M. Vázquez, J. Liu, S. Marczak, Z. Slouka, H. C. Chang, D. Diamond, and D. Brabazon, Biomicrofluidics, 8, 052112 (2014).

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10. S. O. Kelley, C. A. Mirkin, D. R. Walt, R. F. Ismagilov, M. Toner, and E. H. Sargent, Nat. Nanotech, 9, 969 (2014).

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Med. Diagnostics, 5, 381 (2011).

13. Electrogenerated Chemiluminescence, A. J. Bard Editor, Marcel Dekker, New York (2004).

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Chem., 2, 359 (2009).

15. J. Das and S. O. Kelley, Anal. Chem., 83, 1167 (2011).

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18. A. Fragoso, D. Latta, N. Laboria, et al.. Integrated microfluidic platform for the electrochemical detection of breast cancer markers in patient serum samples. Lab on a Chip, 11, 625 (2011).

19. B. V. Chikkaveeraiah, V. Mani, V. Patel, J. S. Gutkind, and J. F. Rusling, Biosens. Bioelectron. 26, 4477 (2011).

20. R. Malhotra, V. Patel, B. V. Chikkaveeraiah, B. S. Munge, S. C. Cheong, R. B. Zain, M. T. Abraham, D. K. Dey, J. S. Gutkind, and J. F. Rusling, Anal. Chem., 84, 6249 (2012).

21. C. K. Dixit, K. Kadimisetty, B. Otieno, C. Tang, S. Malla, C. E. Krause, and J. F. Rusling, Analyst, 141, 536 (2016).

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23. C. E. Krause, B. A. Otieno, G. W. Bishop, P. G. Choquette, R. V. Lalla, D. E. Peterson, and J. F. Rusling, Anal. Bioanal. Chem., 407, 7239 (2015).

24. C. E. Krause, B. A. Otieno, A. Latus, R. C. Faria, V. Patel, J. S. Gutkind, and J. F. Rusling, ChemistryOpen, 2, 141 (2013).

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27. G. W. Bishop, J. E. Satterwhite-Warden, I. Bist, E. Chen, and J. F. Rusling, ACS Sensors, 1, 197 (2016).

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Anodic Olefin Coupling Reactions: A Mechanism Driven Approach to the Development of New Synthetic Tools

by Kevin D. Moeller

W

hile organic electrochemistry has long held promise as a synthetic tool,1 it has remained vastly underutilized.2-4 For example, electrochemistry is seldom employed by the “mainstream” organic synthesis community for the construction of complex molecules, the generation of scaffolds to serve in the development of new drug candidates, or for the diversification of those scaffolds.

Accordingly, electrochemistry for all of its synthetic promise has made little impact on how we approach synthetic challenges that arise on the chemistry-biology interface. This should not be the case, especially at a time when we are becoming increasingly aware of the impact chemistry has on our environment. Electrochemistry has the ability to conduct a vast array of oxidation and reduction reactions without utilizing stoichiometric chemical reagents and without generating the associated waste products. At the same time, it can conduct those oxidation and reduction reactions on substrates with a wide range of oxidation and reduction potentials without having to change the reaction conditions, a situation that enables structure reactivity studies to be conducted on the highly reactive intermediates often involved in the reaction. Hence, the use of electrochemistry not only has the potential to improve the environmental impact of existing redox transformations, but also the potential to teach us about how such reactions proceed in a manner that will allow us to discover and develop entirely new chemical transformations. So, why is electrochemistry lagging behind in its adoption by the larger synthetic community?

Historically, there have been two primary answers to this question; one largely a misperception, and one a gap in understanding. The misperception is that electrochemistry requires expensive, specialized equipment that is not available to most synthetic chemists. While industrial scale-ups and selected electrochemical reactions may require such equipment, the vast majority of electrochemical synthetic methods do not. For example, the very simple reaction setup in illustrated in Fig. 1 has been used to drive both the direct oxidation of organic substrates having oxidation potentials that range from +1.1 V vs. Ag/AgCl to +2.0 V vs. Ag/AgCl,5 as well as a series of indirect oxidations where oxidants such as Ce(IV), Os(VIII), Ru(VII), Cu(II), Pd(II), and Sc(III) have all been employed as catalysts.6 For this setup, visible light (sunlight works just fine), a simple photovoltaic, a couple of wires, and a pair of carbon rods are used to pass a constant current of electricity through the reaction. In such a “constant current” reaction setup, the working potential at the anode climbs until it matches that of the substrate in solution with the lowest oxidation potential. The potential then remains at that point until the substrate at the electrode surface is consumed. At that point, the potential begins to climb again. However, with lower current densities a direct electrolysis reaction can be pushed to 95% completion without any loss in selectivity. For an indirect electrolysis, the mediator serves as a catalyst. It is never consumed, and the selectivity is never lost.

So for any reaction conducted with the setup shown in Figure 1, the potential at the anode will automatically adjust to whatever substrate is in solution leading to the selective oxidation of that substrate.7 Other approaches to the use of very simple electrochemical reaction equipment have also been reported with equal success.8 This is not to say that every electrochemical reaction should be run in such a simple manner, but rather to point out that electrochemical methods can be explored and utilized by synthetic chemists with no equipment-related impediment.

The gap in understanding that hinders the adoption of electrochemical methods is more significant. For most synthetic chemists, electrochemical methods are new. This leads to questions about the design and implementation of a successful reaction, the optimization of reactions that initially do not afford high yields or the desired product, and the role electrolyte, current density, and double layers play in the reactions. In other words, what are the “rules of the game” that a synthetic chemist needs to know in order to get started on the implementation of an electrochemical method? These questions give the impression that a chemist interested in using electrochemistry must undertake a significant learning curve before even starting.

Fortunately, it is not that daunting. Good synthetic methods are often derived from good physical organic chemistry, and electrochemistry is no different. A synthetic chemist can start exploring the reactions with little background and then utilize what they know about organic chemistry to guide their efforts. The development of anodic cyclization reactions provides an excellent backdrop for illustrating this point, and it is the purpose of this paper to highlight a few of the examples that have helped shape the way we thinking about the exploration, development, and utilization of new electrochemical methods.

Anodic cyclization reactions (Scheme 1) are intriguing synthetic transformations because they oxidize a normally nucleophilic olefin in order to reverse its polarity and generate a reactive radical cation intermediate that is then trapped by a second nucleophile.9,10 The loss of a second electron from the cyclic intermediate generated followed by either solvent trapping or another chemical transformation (loss of a silyl group, etc.) leads to a new product that has retained the functionality used to initiate the reaction. The presence of this functionality can be used to further transform the product in subsequent synthetic steps.11-20 The reaction is also mechanistically interesting because it offers an opportunity to systematically study the chemistry of reactive radical cation intermediates under net oxidative conditions.21-44 (continued on next page)

Fig. 1. A simple constant current electrolysis setup.

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Moeller

(continued from previous page)

To capitalize on these opportunities, use of the constant current (galvanostatic) electrolysis conditions is both ideal and essential. The method is ideal because it is very simple and requires no reference electrode.1 This makes the method both practical and easy to adopt by others. Second, the substrates explored in connection with Scheme 1 have had potentials that range from +0.6 V to +2.0 V vs. Ag/AgCl. At times, the oxidation potential of the substrate and product for the reactions has differed by only 100 mV. Hence, a systematic study of the substrates was not possible using a chemical reagent or even an existing family of chemical reagents. A high potential oxidant compatible with the entire range of substrates would not afford the selectivity needed

Scheme 1. The general format of an oxidative cyclization.

Scheme 2. Reactions with allyl- and vinylsilanes.

54

to avoid product over-oxidation for substrates with lower oxidation potentials. An oxidant capable of the 100 mV selectively needed for the selective oxidation of a substrate would not be compatible with the range of substrates used. The use of a combination of oxidants would complicate any mechanistic conclusions reached by forcing changes to the overall reaction conditions. The use of constant current electrolysis for the study avoided all of these problems. In each case, the potential at the anode simply adjusted to that of the substrate and then remained there ensuring the selectivity of the reaction. In this way, a standard set of conditions could be used for each of the substrates.

Allyl- and Vinylsilanes and the Initial Defining of a Mechanistic Model While cyclizations that coupled two enol ethers were used to rapidly demonstrate the synthetic viability of the reactions in Scheme 1, it was the development of the initially far more problematic examples using allylsilane and vinylsilane coupling-partners that taught us how to think about the reactions.45-47 Three representative cases are shown in Scheme 2. For the enol ether – enol ether coupling reactions, almost any solvent and electrolyte combination proved compatible with a successful cyclization. However, when the optimized conditions using a Pt-anode were attempted with an allylsilane-based substrate (Scheme 2, equation 1) the reaction led only a 46% yield of the desired product (6).45 Attempts to probe the reason for the low yield using cyclic voltammetry data were not helpful. The substrate oxidized just fine and gave rise to a voltammetry curve that looked very much like the one obtained for the very successful enol ether – enol ether coupling reactions. Fortunately, a classic physical organic chemistry approach to the problem resolved the issue. For any reaction involving a reactive intermediate, the key questions are, what did it form and what do those products imply about the mechanism by which the reactive intermediate decomposed? For the oxidation of 5, one of the minor products generated, the cyclic vinylsilane (7), was particularly informative. Vinylsilane 7 was formed from the loss of a hydrogen atom from the carbon bearing the silicon group. Its generation was surprising since the proposed cyclization leading to a cation at the terminating end of the cyclization would place that cation beta to the silyl group. Intermediates of this nature are known to rapidly eliminate the silyl group leading to the formation of a monosubstituted olefin (6). This suggested that the intermediate at the terminal end of the cyclization alpha to the silyl group was not a cation but rather a radical. A radical intermediate might undergo the loss of a neighboring hydrogen atom along with a variety of other transformations. If this were the case, then a rapid second oxidation would be needed to convert this radical to a cation and in so doing push the reaction toward the desired silyl-based elimination.

To test this idea, the anode used for the oxidation of 5 was switched from platinum to a high surface area reticulated vitreous carbon (RVC). Suggestions in the literature implied that the fouling of Pt-anodes during organic reactions makes it difficult to conduct two electron oxidations at Pt. This was not as much of a problem when a high surface area carbon anode was employed. In practice, the oxidation of 5 at an RVC anode led to an 84% isolated yield of the desired product 6. Our first major challenge was solved, and our first mechanistic insight into the nature of radicalcation derived carbon-carbon bond formation gained.

The hypothesis that the reactions led to a radical at the terminating end of the cyclization was quickly supported with the substrates The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

Scheme 3. A mechanistic model.

Scheme 4. Alcohol trapping reactions.

shown in Scheme 2, equation 2.46 In this case, the parent cyclization (R = H) led to a complex mixture of both five- and six-membered ring products. The silyl group was then incorporated knowing that silicon groups stabilize β-carbocations but α-radicals.48 If the cyclization led to a cation on the terminal end, then the incorporation of the silyl group would favor 5-membered ring products. If it led to a radical at the terminating end, then the presence of the silyl group would favor 6-membered ring products. The oxidation of vinylsilane substrate 8 led to exclusive formation of six-membered ring products verifying the presence of a radical at the terminating end of the cyclization.

Other reactions with vinylsilane-based substrates showed that the cyclizations were reversible.46 At the same time, cyclizations with allylsilane terminating groups (Scheme 2, equation 3) were proving to be under kinetic control.49 The combination of these reactions gave rise to the mechanistic model for the reactions shown in Scheme 3 and the general idea of a cyclization that was under kinetic control if the rate of the second oxidation was faster than the reverse reaction and thermodynamic control if the rate of the reverse reaction was faster than the second oxidation.

The third reaction shown in Scheme 2 was also important because of an initial failure.49 The cyclization worked very well as long as the allylic alcohol in the substrate was protected. The reaction proceeded in a predictable fashion through a chair-like transition state. It afforded a high yield of the cyclized product and the quaternary carbon without any elimination of the allylic oxygen. However, when the allylic alcohol was not protected, the reaction afforded none of the desired product.

This was a surprise since the successful cyclization was run in methanol solvent. If the presence of an alcohol interfered with the cyclization, then why didn’t the methanol?

The answer to this question lies in understanding the role of electrolyte in the reaction and the formation of an electrochemical double layer (outer Helmoltz layer from a physical chemistry perspective) at the surface of the anode. The electrolyte in an electrochemical reaction is used to balance the charges generated at the electrodes. The positive ion of the electrolyte serves as the counter-ion for anions generated at the cathode and the negative ion of the electrolyte serves as the counter-ion for cations generated at the anode. Without these counter-ions, a buildup of charge at the electrodes occurs causing resistance in the cell. The electrolyte relieves this problem. However, it also alters the nature of the solution at the surface of the electrodes. When a positively charged anode is inserted into an electrolyte solution, it attracts a layer of negatively charged electrolyte which in turn attracts a second layer of positively charged electrolyte. This process continues out further from the anode, but as the distance from the anode increases the relative order of the layers decreases.

Hence, the two layers close to the electrode surface have the greatest influence on the reaction. An opposite scenario plays out on the surface of the cathode.

For the reaction shown in Scheme 2, equation 3, this is important because the anodic oxidation and subsequent cyclization reaction take place in the organized double layer at the surface of the anode. The double layer both slows diffusion and serves to exclude solvent from the surface near the electrode. Both factors favor intramolecular reactions relative to solvent trapping.50,51 For the radical cation derived from 11, intermolecular trapping by methanol solvent in the double layer is slow relative to the cyclization. However, when the alcohol is dragged into the double layer as part of the substrate, intramolecular trapping of the radical cation by that alcohol is very fast, an observation that has been confirmed by subsequent competition studies.52 The consequence for the reaction shown in Scheme 2 was the need to protect the alcohol before the anodic oxidation. This ensured that the reaction had the time needed for it to proceed down its intended path.

Trapping with Heteroatoms, the Curtin-Hammett Principle, and More about Double Layers It did not take long for the mechanistic observations made in connection with the reaction shown in Scheme 2, equation 3 to pay further synthetic dividends (Scheme 4). For the synthesis of (+)-nemorensic acid (Scheme 4, equation 1), the anodic oxidation of a dithioketene acetal derivative13 was used to generate a radical cation that was in turn intentionally trapped by an alcohol nucleophile. The reaction led to the formation of a functionalized tetrahydrofuran ring with control over the relative stereochemistry of a tetrasubstituted carbon. Related studies defined the stereochemical preferences for the reaction,14 and demonstrated that the trapping of a non-polar radical cation like the favored heteroatomic nucleophiles while the trapping of a more polar radical cation favored C-C bond formation.53,54

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More recently, the observation that alcohol cyclizations are fast has been used to aid the formation of difficult carbon-carbon bond forming reactions (Scheme 4, equation 2).55 In this example, the use of a second, alcohol nucleophile in an anodic cyclization enabled the reaction to overcome the barriers associated with the trapping of a radical cation by an allylsilane to simultaneously form a sixmembered ring and a quaternary center. When a methoxy enol ether

Scheme 5. Curtin-Hammett controlled reactions.

was used as the site of radical cation formation, little of the desired product was formed. The cyclization was too slow and the reaction led to elimination and solvent trapping products from the radical cation. By including the additional alcohol nucleophile to rapidly trap the radical cation, the cationic character of the reactive intermediate was removed. This slowed the elimination and solvent trapping reactions and allowed more time for the desired C-C bond formation.

Because alcohol trapping of a radical cation is both exothermic and reversible,56 the temperature of the reaction was lowered in order to keep intermediate 20 closed.

The observation that the alcohol trapping reaction was fast, also led to the design of Curtin-Hammett controlled reactions.57 In this chemistry, it was recognized that intramolecular electron-transfer reactions occur quickly, and that the product from an anodic cyclization was not simply derived from the site of the initial oxidation but rather by how fast a given intermediate leads to product. Consider the reaction shown in Scheme 5, equation 1. The group with the lowest oxidation potential in substrate 22 is the dithioketal. Oxidations of dithioketals typically lead to cleavage of the dithioketal.58 However, in this case the radical cation generated by the initial oxidation is rapidly (and most likely reversibly) reduced by the neighboring enol ether to form a new radical cation that is then trapped by the alcohol nucleophile. The result is a classic CurtinHammett situation where a rapid equilibrium between reactive intermediates is drained to product by the fastest follow-up reaction. The reaction was synthetically intriguing because the location of the dithioketal channeled the oxidation toward one of two nearly identical enol ethers in the substrate.

Extension of this chemistry to a carboncarbon bond forming reaction again relied on a consideration of the electrolyte and the role of the double layer in shaping the course of a chemical reaction.59 In Scheme 5, equation 2, the coupling of two enol ethers in the presence of a dithioketal is illustrated. Once again, the lowest oxidation potential in the substrate was the dithioketal. However, in this case trapping of the thiol radical cation by methanol competed with the enol ether radical cation derived cyclization, especially when lithium perchlorate was used as the electrolyte. When a “greasier” electrolyte was employed, carboncarbon bond formation dominated the reaction.

The choice of the electrolyte dictated the nature of the double layer formed at the anode and thereby dictated the local environment in which the synthetic transformation took place.

When the more polar lithium perchlorate was used as the electrolyte, a high concentration of methanol was present in the double layer and solvent trapping was relatively fast. When the much less polar tetraethylammonium tosylate was used, the double layer excluded the polar methanol solvent50,51 favoring the intramolecular cyclization. So, the choice of an electrolyte for the reaction was a result of examining the competitive mechanistic pathways that operate during the reaction and then using solubility to favor the pathway that was most desirable.

Scheme 6. C-glycosides and the effect of electrolyte.

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Combining the Concepts of Reversible Cyclizations, Removal of a Second Electron, and Electrolyte Considerations to Optimize the Formation of a C-glycoside The observation made about the choice of electrolyte and its effect on solubility made above is not an isolated example. In Scheme 6, equation 1, the choice of lithium perchlorate as the electrolyte proved critical for optimization of the reaction used to generate a C-glycoside.

When tetraethylammonium tosylate was used as the electrolyte, the reaction led to poor conversion of the substrate even when excess current was utilized. In this case, the substrate itself is very polar. The use of a non-polar electrolyte and formation of a non-polar double layer not only excluded methanol from the region proximal to the electrode, but also the substrate. The use of a more polar electrolyte allowed the polar substrate to better approach the anode and enabled the reaction to proceed in high yield and excellent conversion.

The second reaction shown in Scheme 6,61 provides an excellent example of how many of the physical organic considerations described above can come into play when optimizing an electrochemical reaction. In this case, it was the concentration of the electrolyte that helped define the current efficiency of the reaction. To understand this observation, it is important to consider the mechanistic model forwarded in Scheme 3.56 Specifically, the notion that the cyclizations are reversible if the rate of the second oxidation (k2) is slow. For the reaction originating from a styrene derivative (Scheme 7), the cyclization led to a benzylic radical that was oxidized slowly. The resulting intermediate (an equilibrium between 34 and 35) was stable enough to diffuse to the cathode in the undivided cell and get re-reduced to the substrate (33). The result was a reaction that remained clean, but consumed too much current.

When the reaction cell was divided, the substrate was consumed but the reaction yield did not improve. This was consistent with a slow second oxidation and the formation of a radical intermediate that did not have a clear path to product formation. Radical intermediates that do not have a productive reaction pathway initiate lots of pathways.

What was needed was a faster second oxidation that would push the reaction toward the desired product.

There were two ways to address this issue. The first was to modify the substrate so that the cyclized, benzylic radical would have a lower oxidation potential. The addition of a methoxy group to position R in Scheme 7 led to an 83% yield of the desired product after the passage of only 2 F/mole of charge. While this approach worked very well, one cannot always adjust the substrate to make a reaction work. For the example shown in Scheme 6, equation 2, the substrate was dictated by the biphenyl substituted C-glycoside needed. The substrate could not be changed.

The key to optimizing this example was to recognize that the oxidation of intermediates like 35 in Scheme 7 lead to the generation of cations (36). Anything that stabilizes the cation will aid in removal of the electron. To this end, an increase in the concentration of the counter ion for the cation will help stabilize the cation as it forms, a situation that lowers the oxidation potential of the radical. So an increase in the concentration of the electrolyte should aid the overall reaction. This proved to be the case for the reaction shown in Scheme 6, equation 2 where a ten-fold increase in the concentration of electrolyte led to a dramatic improvement in current efficiency.

While the reaction illustrated was not optimized further, it should be noted that for reactions where a high concentration of electrolyte is required, recyclable composite62,63 or polymerbased electrolytes64,65 can be used to improve the sustainability of the process.

Generality – Using the Same Overall Approach to Solve an Entirely Different Challenge Many of the approaches described above are general and can be applied to a very diverse set of synthetic challenges. For example, the same consideration of the chemical processes that occur at or near an electrode, and how the relative rates of those processes can be adjusted, that have been used to develop new synthetic methods for the construction of complex molecules can also be used to develop methods for the construction of complex, carefully controlled surfaces on addressable microelectrode arrays.66 Microelectrode arrays are an intriguing platform for the “real-time” analysis of small molecule libraries and their binding to protein targets (Scheme 8). In this application, the members of a small molecule library are placed or synthesized by specific addressable electrodes in a microelectrode array. The electrodes are then used to monitor the current associated with a redox mediator in solution. When a receptor added to the solution above the array binds a molecule on the surface of the array, it changes the ability of the mediator to reach the electrode below and alters the current being monitored. The change in current is detected indicating the onset of the binding event. The key challenge to the experiment is placing or synthesizing the molecules in the library proximal to specific addressable electrodes in the array. This is especially true when the arrays have a density of 12,544 electrodes per square centimeter.

The challenge posed above can be solved by using the electrodes themselves to conduct synthetic reactions on the arrays. To do so requires the juggling of two reaction rates: one for a reaction that makes a chemical reagent or catalyst at the electrode and the second for a reaction that destroys the same chemical reagent or catalyst in the solution above the electrode. The best way to understand this solution is to look at a specific example (Scheme 9).67 In this example, cysteine is added site-selectively to specific electrodes in an array that was first coated with a borate ester functionalized diblock copolymer.68 The N-terminus of the cysteine was then used for subsequent coupling reactions on the array. Our focus here will be the site-selective placement of the cysteine group onto the array.

The borate ester coating on the array was used to provide attachment sites for the cysteine above every electrode in the array. The polymer was used instead of a self-assembled monolayer strategy for coating the electrodes because it provides greater chemical and long-term stability to the surface. Once the polymer was in place, the borate esters above selected electrodes were replaced with the thiol nucleophile in cysteine by using the electrodes to oxidize a Cu(I)-precursor and generate a Cu(II)-reagent. The Cu(II)-reagent mediated a Chan-Lam type coupling reaction between the arylboronates on the electrode and the thiol nucleophile.69 (continued on next page)

Scheme 7. Mechanism of C-glycoside formation.

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Scheme 8. Microelectrode array approach to monitoring receptor – ligand interactions.

reagent was generated, the distance Cu(II) migrated away from any electrode used for its generation could be manipulated.

In many ways, the control of spatial selectivity on the array is the same as the control of chemoselectivity in reactions like the one illustrated in Scheme 5, equation 2. Both selectivities were obtained by consideration of the reactions that occur at or near the electrode surface and then manipulating the conditions used for the reaction to adjust their relative rates. If you want to slow an intermolecular reaction relative to an intramolecular one in the preparative chemistry (Scheme 5, equation 2), then adjust the electrolyte so that it lowers the concentration of one of the reagents and slows the intermolecular reaction. If you want to improve the site-selectivity of an array reaction, then lower the current so that you lower the concentration of active reagent being generated.

They key to both reactions is to understand the physical organic chemistry involved in the process.

Conclusions

Scheme 9. Site-selective array chemistry.

To accomplish the reaction in a site-selective fashion, the array is initially treated with a catalytic amount of CuSO4 and an excess of the fluorescently labelled cysteine derivative. A small amount of the thiol present reduced the CuSO4 to form the solution phase Cu(I)-reagent and a dithiane product (which can also serve as a substrate for the Chan-Lam coupling). The borate ester surface is stable to Cu(I), so at this point no reaction occurred on the surface of the array. Selected electrodes in the array were then used as anodes by setting them to a potential positive relative to a Pt-counter electrode. As in the earlier constant current electrolysis, the potential at the selected anodes climbed until it matched that needed for the substrate present; in this case the Cu(I). For the image shown in the Scheme, a C-pattern of electrodes were used.

Of course, generating the active Cu(II)-reagent at the electrode represents only one half of the strategy. For the array shown in Scheme 9, the electrodes are separated by only 33 μm. If left unchecked, a reagent generated at one electrode will quickly migrate to, and cause reactions on, the surface above the neighboring electrodes. For this reason, all array reactions are conducted in the presence of a second chemical reaction that destroys the reagent being generated at the electrodes. This confines the reagent to the sites used for the reaction.

For the reaction shown in Scheme 9, this “confining-reaction” was the reaction used to pacify the initial CuSO4 reagent, namely a reaction between the Cu(II) reagent generated at the electrodes and excess thiol in solution to form Cu(I) and the dithiane. With the two reactions in place, the rate of Cu(II) generation on the array was adjusted relative to the rate of Cu(II) consumption by raising and lowering the current used to generate the Cu(II). By controlling the rate at which the active 58

In the end, the “rules of the game” that organic chemists need to know in order to utilize and design electrochemical reactions are the same ones they have always used. For the vast majority of electrochemical reactions, it can be assumed that the electrons are transferred and that the desired reactive intermediate is made.

What needs to be controlled is what happens to that reactive intermediate. That is accomplished by the same techniques used to control the chemistry of any reactive intermediate. First, gain insight into the mechanism of the reactions triggered by the reactive intermediate, and then, manipulate the conditions of the reaction to channel the intermediate toward a desirable pathway. In other words, the development and optimization of new electrochemical synthetic methods begins by getting the organic chemistry correct. © The Electrochemical Society. All rights reserved. DOI: 10.1149/2.F07162if.

Acknowledgements We thank the National Science Foundation (CHE-1463913, CBET1262176) for their generous support of our work.

About the Author Kevin D. Moeller joined the chemistry faculty at Washington University in St. Louis in 1987, and he has been Professor of Chemistry since 1999. He earned a BA degree in Chemistry from the University of California – Santa Barbara in 1980 and then his PhD degree in Organic Chemistry (Professor R. Daniel Little) from the same institution in 1985. He was an NIH Postdoctoral Fellow at the University of Wisconsin – Madison (Professor Barry M. Trost) from 1985 to 1987. From The Electrochemical Society he received the Manuel M. Baizer Award in Organic Electrochemistry in 2016, and from The American Chemical Society he received the “St. Louis Award” for his contributions to Chemistry in 1997. He can be reached at moeller@wustl.edu.

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t ech SEC TION highligh NE WS ts Chicago Section On April 5, 2016, the Chicago Section convened at Argonne National Laboratory for its spring 2016 meeting. Argonne National Laboratory is located in Lemont, IL, and is a multidisciplinary science and engineering research facility that is home to thousands of scientists and fifteen research divisions. The meeting attendees were offered the opportunity to tour the Advanced Photon Source and Argonne’s Center for Transportation Research (CTR). CTR is involved in

accelerating the development and deployment of vehicle technologies that help reduce U.S. petroleum consumption and greenhouse gas emissions. The meeting ended with Deyang Qu, from the University of Wisconsin-Milwaukee, presenting on the development of a method used to accurately identify each polysulfide ion involved in the redox mechanism of lithium-sulfur batteries.

Chile Section The Chile Section sponsored a summer school in electrochemistry in January 2016. This was the third version of this annual offering. The course was attended by graduate students from several universities of the Santiago region. The course has become a tradition offered by the faculty of chemistry and biology of the University of Santiago de Chile (USACH). It was organized by Ricardo Salazar and involved

several faculty members from USACH, postdocs, and guest speakers from other universities of Latin America. The opening plenary lecture was delivered by Juan Manuel Peralta from the University of Guanajuato, Mexico and the closing lecture was delivered by Carlos Martinez-Huitle from the Federal University of Rio Grande do Norte, Natal, Brazil.

Attendees of the summer school in electrochemistry sponsored by the ECS Chile Section.

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Send your news to: ecs@electrochem.org

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t ech SEC TION highligh NE WS ts Japan Section The Japan Section of The Electrochemical Society recently sponsored an award in partnership with the Tokai Branch of the Electrochemical Society of Japan (ECSJ). The ECSJ Tokai Branch Young Researcher Award was given to Taro Uchida, Assistant Professor, Interdisciplinary Cluster for Cutting Edge Research, Center for Energy and Environmental Science at the Shinshu University. Dr. Uchida was awarded for his research paper “Probing the Electrochemical Interface by ATR-SEIRAS Using Polarized Radiation,” presented at the 46th Annual Meeting of Union of Chemistry-Related Societies held on November 7, 2015 at the Mie University, Japan. The young researcher award was presented to Dr. Uchida in a ceremony held on February 3, 2016.

Tarou Uchida (right), the Young Researcher Award Winner, together with Takashi Sugiura, Chair of the Tokai Branch of the Electrochemical Society of Japan.

Korea Section The Korea Section symposium, organized by Yung-Eun Sung, Soo-Kil Kim, and Jong Hyun Jang, was held on April 7, 2016, at Kimdaejung Convention Center in Gwangju, Korea, concurrently with spring meeting of the Korean Electrochemical Society (KECS). This was the second ECS Korea Section Symposium on Electrochemical CO2 Conversion. It was composed of six talks on the electrocatalysts and systems for electrochemical reduction of CO2.

At the end of the symposium, Changshin Jo received the 2016 Student Award of the Korea Section with a cash prize of $500 from the Society. During the symposium, Mr. Jo also presented his work titled “Designed Porous Materials for Energy Storage Applications.”

He recently received his PhD in Chemical Engineering from Pohang University of Science and Technology (POSTECH), Korea. His current research interest is the development of hierarchically porous materials for energy storage applications including lithium-sulfur and -oxygen batteries. He has combined block copolymer self-assembly with inorganic sol-gel chemistry to fabricate high performance electrodes, constructed of porous inorganic materials (e.g., carbon, metal -oxides, -nitrides, -sulfides, and composites).

The next award will be presented at the spring symposium of the section in 2017.

Changshin Jo (right) received the 2016 Student Award of the Korea Section from Yongkeun Son, KECS President (left)

Twin Cities Section On Friday, April 29, 2016, the Twin Cities Section hosted a short course, Introduction to EIS, in Shoreview, Minnesota. Mark Orazem, Distinguished Professor of Chemical Engineering at the University of Florida, Fellow of ECS, and recognized expert on impedance spectroscopy, served as the instructor. Metrohm USA served as a

sponsor for the program. Kristin Stafford, Electrochemistry Sales Representative for Metrohm USA, was on site to demonstrate an electrochemical impedance spectroscopy test equipment and the Autolab test and analysis software to the attendees.

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AWARDS NE W MEMBERS Program

Awards, Fellowships, Grants ECS distinguishes outstanding technical achievements in electrochemistry, solid-state science and technology, and recognizes exceptional service to the Society through the Honors & Awards Program. Recognition opportunities exist in the following categories: Society Awards, Division Awards, Student Awards, and Section Awards.

ECS recognizes that today’s emerging scientists are the next generation of leaders in our field and offer competitive Fellowships and Grants to allow students and young professionals to make discoveries and shape our science long into the future.

See highlights below and visit electrochem.org for further information.

ECS Society Awards The Carl Wagner Memorial Award was established in 1980 to recognize a mid-career achievement and excellence in research areas of interest of the Society, and significant contributions in the teaching or guidance of students or colleagues in education, industry, or government. The award consists of a silver medal, wall plaque, Society Life membership, complimentary meeting registration, and travel assistance of up to $1,000.

Materials are due by October 1, 2016.

The Olin Palladium Award was established in 1950 to recognize distinguished contributions to the field of electrochemical or corrosion science. The award consists of a palladium medal, wall plaque, $7,500 prize, ECS Life Membership, and complimentary meeting registration.

Materials are due by October 1, 2016.

Fellow of The Electrochemical Society was established in 1989 as the Society’s highest honor in recognition of advanced individual technological contributions in the field of electrochemical and solidstate science and technology, and active ECS membership. The award consists of an appropriately worded scroll and lapel pin. Go to www. electrochem.org/society to start the nomination process.

Materials are due by February 1, 2017.

The Henry B. Linford Award was established in 1981 to recognize excellence in teaching in subject areas of interest to the Society. The award consists of a silver medal and a plaque that contains a bronze replica, the sum of $2,500, complimentary meeting registration for award recipient and companion, a dinner held in recipient’s honor during the designated meeting, and Life Membership.

Materials are due by April 15, 2017.

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The Vittorio de Nora Award was established in 1971 to recognize distinguished contributions to the field of electrochemical engineering and technology.

The award consists of a gold medal and a plaque that contains a bronze replica thereof, both bearing the recipient’s name, the sum of $7,500, complimentary meeting registration for award recipient and companion, a dinner held in recipient’s honor during the designated meeting, and Life Membership.

Materials are due by April 15, 2017.

ECS Division Awards The Dielectric Science and Technology Division Thomas D. Callinan Award was established in 1967 to encourage excellence in dielectrics and insulation investigations, to encourage the preparation of high-quality science and technology papers and patents, to encourage publication in the applicable ECS journal, and to recognize outstanding contributions to the field of dielectric science and technology. The award consists of a scroll, and a $1,500 prize.

Materials are due by August 1, 2016.

The Electronics and Photonics Division Award was established in 1969 to encourage excellence in electronics research and outstanding technical contribution to the field of electronics science. The award consists of a scroll, a $1,500 prize and the choice of up to $1,000 of un-reimbursed expenses to facilitate travel to the designated meeting or ECS life membership.

Materials are due by August 1, 2016.

The Energy Technology Division Research Award was established in 1992 to encourage excellence in energy related research and to encourage publication in the applicable ECS journal. This award consists of scroll, check for $2,000, and membership in Energy Technology Division for as long as an ECS member.

Materials are due by September 1, 2016.

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

AWARDS NE W AWA MEMBERS PROGRAM RDS New to the ECS Honors & Awards Program ECS Battery Division Postdoctoral Associate Research Award Sponsored by MTI Corporation and the Jiang Family Foundation Visit www.electrochem.org for more details.

The Energy Technology Division Supramaniam Srinivasan Young Investigator Award was established in 2011 to recognize and reward an outstanding young researcher in the field of energy technology. Such early recognition of highly qualified scientists is intended to encourage especially promising researchers to remain active in the field. This award consists of scroll, check for $1,000, and free meeting registration.

Materials are due by September 1, 2016.

Student Awards The Georgia Section Outstanding Student Achievement Award was established in 2011 to recognize academic accomplishments in any area of science or engineering in which electrochemical and/or solid state science and technology is the central consideration. The award consists of a $500 prize and is presented at a designated Georgia Section meeting.

Materials are due by August 15, 2016.

The Energy Technology Division Graduate Student Award was established in 2012 to recognize and reward promising young engineers and scientists in fields pertaining to this Division. The award is intended to encourage the recipients to initiate or continue careers in this field.

The award consists of a scroll, a $1,000 prize, and complimentary student registration. The recipient(s) is required to present a lecture in an ETD-sponsored symposium at the designated Society meeting where the award is presented. In addition, the recipient receives unreimbursed travel expenses of up to $1,000 to facilitate attendance.

Materials are due by September 1, 2016.

The Nanocarbons Division Richard E. Smalley Research Award was established in 2006 to encourage excellence in fullerenes, nanotubes and carbon nanostructures research. The award is intended to recognize, in a broad sense, those persons who have made outstanding contributions to the understanding and applications of fullerenes. The award consists of a scroll, a $1,000 prize, and assistance up to a maximum of $1,500 to facilitate meeting attendance at which the award is to be presented.

Materials are due by September 1, 2016.

The IEEE Division H. H. Dow Memorial Student Achievement Award was established in 1990 to recognize promising young engineers and scientists in the field of electrochemical engineering and applied electrochemistry.

This award was made possible by a gift from The Dow Chemical Company Foundation and is intended to encourage the recipient to continue his career in electrochemical engineering or applied electrochemistry. The award consists of a scroll and a $1,000 prize to be used for expenses associated with the recipient’s education or research project: tuition, books, equipment, or supplies.

Materials are due by September 15, 2016.

The Corrosion Division Herbert H. Uhlig Award was established in 1972 to recognize excellence in corrosion research and outstanding technical contributions to the field of corrosion science and technology. The Award will consist of $1,500 and an appropriately worded scroll and the recipient may receive (if required) financial assistance from the Corrosion Division toward travel expenses to the Society meeting at which the award is presented.

Materials are due by December 15, 2016.

The IEEE Division Student Achievement Awards were established in 1989 to recognize promising young engineers and scientists in the field of electrochemical engineering. The awards are intended to encourage the recipients to initiate or continue careers in this field. The award consists of a scroll and a $1,000 prize. One year after receiving the award, each recipient will be requested to submit to the Division Chair a written summary of the research accomplished during the year.

Materials are due by September 15, 2016.

The High Temperature Materials Division J. Bruce Wagner, Jr. Award was established in 1998 to recognize a young Society member who has demonstrated exceptional promise for a successful career in science and/or technology in the field of high temperature materials. The award consists of an appropriately worded scroll and the sum of $1,000. The recipient may receive (if required) complimentary registration and up to $1,000 in financial assistance toward travel expenses to the Society meeting at which the award is made.

Materials are due by January 1, 2017.

The Korea Section Student Award was established in 2005 to recognize academic accomplishments in any area of science or engineering in which electrochemical and/or solid state science and technology is the central consideration. The award consists of a $500 prize and is presented at a designated Korea Section meeting. At that time, the recipient may be requested to speak on a subject of major interest to him/her in the field of electrochemical and/or solid state science and technology.

Materials are due by September 30, 2016.

Section Awards The Europe Section Heinz Gerischer Award was established in 2001 to recognize an individual or a small group of individuals (no more than 3) who have made an outstanding contribution to the science of semiconductor electrochemistry and photoelectrochemistry including the underlying areas of physical and materials chemistry of significance to this field. The award consists of a scroll and 2,000 EUR prize and, if required, financial assistance for un-reimbursed travel expenses incurred to receive the Award, not to exceed 1,000 EUR. Materials are due by September 30, 2016.

The Corrosion Division Morris Cohen Graduate Student Award was established in 1991 to recognize and reward outstanding graduate research in the field of corrosion science and/or engineering. The award consists of a certificate and the sum of $1,000. The award, for outstanding Masters or PhD work, is open to graduate students who have successfully completed all the requirements for their degrees as testified to by the student’s advisor, within a period of two years prior to the nomination submission deadline.

Materials are due by December 15, 2016.

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

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NE W MEMBERS ECS is proud to announce the following new members for January, February, and March 2016.

Active Members Parama Chakraborty Banerjee, Melbourne, Victoria, Australia Sangki Chun, Daejeon, South Korea Jared Craggs, Mentor, OH, USA Hanping Ding, Golden, CO, USA Magdalena Dudek, Cracow, Poland Salim El Kazzi, Heverlee Leuven, Belgium Michael Gorman, South Glastonbury, CT, USA Matt Graham, Corvallis, OR, USA John Gustafson, Chandler, AZ, USA Phuc Ha, Pullman, WA, USA Liang Hong, Houston, TX, USA John Hryniewicz, Columbia, MD, USA Hiroshi Imoto, Utsunomiya, Tochigi, Japan Nicole Iverson, Lincoln, NE, USA B. Reeja Jayan, Pittsburgh, PA, USA Stephan Keller, Kongens Lyngby Sealand, Denmark Soorathep Kheawhom, Patumwan Bangkok, Thailand Jonghoon Kim, Gwangju, South Korea Ivoyl Koutsaroff, Apopka, FL, USA Gyozo Lang, Budapest, Hungary Anders Laursen, New York, NY, USA Dustin McLarty, Pullman, WA, USA Andries Meijerink, Utrecht, Netherlands Wayne Mercer, Prescott Valley, AZ, USA Katie Moon, Concord, OH, USA Adam Moore, Incline Village, NV, USA Yoon Myung, Saint Louis, MO, USA Simona Onori, Greenville, SC, USA Sinem Ortaboy, Berkeley, CA, USA Chenyun Pan, Atlanta, GA, USA Elizabeth Paul, Urbana, OH, USA Yuan, Ping Pasadena, CA, USA Srivatsava Puranam, Cambridge, MA, USA Debasish Sarkar, Bangalore, KA, India Taro Shimonosono, Kagoshima, Kagoshima, Japan Nicholas Sinclair, Amherst, OH, USA Rajesh Sur, Winston Salem, NC, USA Irina Svir, Paris Ile-de-France, France Elijah Thimsen, Saint Louis, MO, USA Lizhu Tong, Tokyo, Tokyo, Japan Liliana Trevani, Oshawa, ON, Canada Jeff Tsao, Albuquerque, NM, USA Ana Sofia Varela, Berlin, BE, Germany Roseanne Warren, Salt Lake City, UT, USA Jerome Wiedmann, Santa Barbara, CA, USA Gautam Yadav, New York, NY, USA Zheng Yang, Chicago, IL, USA

Student Members Shelby Boyd, Raleigh, NC, USA Arturas Adomkevicius, Liverpool, Merseyside, United Kingdom Rauf Aksu, Ankara, Turkey Maria Al Hajji Safi, Limerick Munster, Ireland

John Alper, Gif-sur-Yvette Allee-de-France, France Aqeel Alrebh, Montreal, QC, Canada M S Amrutha, Chennai, TN, India Alessandra Antonucci, Lausanne, VD, Switzerland Erhan Atci, Pullman, WA, USA Andrew Baker, Los Alamos, NM, USA Mehrdad Balandeh, Limerick Munster, Ireland Zachary Balsinger, Tallahassee, FL, USA Jorge Banda Aleman, Pedro Escobedo, Qro, Mexico Serene Bayram, Montreal, QC, Canada Franky Bedoya-Lora, London, Gtr London, United Kingdom Sepideh Behboudikhiavi, Tehran, Iran Anne Berger, Garching, Germany Erlend Bertheussen, Kgs. Lyngby Hovedstaden, Denmark Brandon Bocklund, Battle Creek, MI, USA Daniel Boehm, Munich, BY, Germany Noah Budin, Ithaca, NY, USA Ian Byrd, Statesboro, GA, USA Alan Campbell, Pittsburgh, PA, USA Corentin Carmignani, Grenoble Rhone Alps, France Ting-Wei Chang, Hsinchu, Taiwan, Taiwan Navid Chapman, Kingston, RI, USA Mathieu Charbonneau, Montreal, QC, Canada Chuan-Hua Chen, Hsinchu, Taiwan, Taiwan Jerry Chen, Seattle, WA, USA Limei Chen, Santa Cruz, CA, USA Ying-Chen Chen, Austin, TX, USA Jen-Hao Chien, Taipei, Taiwan, Taiwan Tazima Chowdhury, Harrison, NJ, USA Hyeseung, Chung, La Jolla, CA, USA Gwenn Cognard, Saint Martin d Heres Isere, France Julio Conde, Madrid, MAD, SPAIN Lei Cong, Houston, TX, USA Elizabeth Corson, East Palo Alto, CA, USA Maria Damaris Cortez Diaz, Puebla, Mexico Jaclyn Coyle, Boulder, CO, USA Stephanie Damas, Tallahassee, FL, USA Andrew Danis, Montreal, QC, Canada Collin Davies, Austin, TX, USA Malak Dayeh, Montreal, QC, Canada Kim De Nolf, Gent Oost-Vlaanderen, Belgium Diana Dector, Santiago de Queretaro, Querétaro, Mexico Kishore Kumar Devarepally, Edinburgh, Scotland Ruchira Dharmasena, Louisville, KY, USA Yuan(Prince) Ding, Saskatoon, SK, Canada Chuancheng Duan, Golden, CO, USA Yueting Duan, Heverlee Flemish Brabant, Belgium Masamitsu Egawa, Muenchen, BY, Germany Carol Ellis-Terrell, Schertz, TX, USA

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Simon Erhard, Munich, BY, Germany Mohsen Esmaily, Gothenburg, Sweden David Fabian, Irvine, CA, USA Noushin Fallahpour, Brighton, MA, USA Ye Fan, Blacksburg, VA, USA Alta Fang, San Diego, CA, USA Sinan Feng, Austin, TX, USA Jasmin Flowers, Virginia Beach, VA, USA Marveh Forghani, New Lambton, New South Wales, Australia Rune Frederiksen, New York, NY, USA Melanie, Freire, Caen cedex 4 Normandy, France Matthew Frith, Lexington, KY, USA Christine Gabardo, Dundas, ON, Canada Maria Garcia Mendez, Ypsilanti, MI, USA Marco Garcia Morales, Toluca, Estado de Mexico, Mexico Samantha Gateman, Montreal, QC, Canada Raziyeh Ghahremani, Athens, OH, USA Arash GhalayaniEsfahani, Milan, Italy Oumaima Gharbi, Paris, France Dean Glass, Los Angeles, CA, USA Abraham Gomez Vidales, Montreal, QC, Canada Jesse Gordon, Hampstead, QC, Canada Alireza Goshtasbi, Ann Arbor, MI, USA Lana Greene, Montreal, QC, Canada Simranjit Grewal, Denair, CA, USA Valeriia Grigel, Ghent East Flanders, Belgium Jan-Philipp Grote, Duesseldorf, NW, Germany Benjamin Groven, Leuven Vlaams-Brabant, Belgium Kieran Halligan, Boston, MA, USA Jackson Harvey, New York, NY, USA Qian He, San Diego, CA, USA Hendrik Heenen, Garching, BY, Germany Kai Henry, College Station, TX, USA Mayra Hernandez-Rivera, Houston, TX, USA Rosa Herrada, Torreon, Mexico Wisit Hirunpinyopas, Manchester, Greater Manchester, United Kingdom David Ho, Cary, NC, USA Hui Huang Hoe, Toronto, ON, Canada Sooji Hong, Los Angeles, CA, USA Peiguang Hu, Santa Cruz, CA, USA Jinchao Huang, New York, NY, USA Yu-Chen Hung, Taipei, Taiwan, Taiwan Monica Hwang, College Station, TX, USA Shinjae Hwang, Piscataway, NJ, USA Luca Imponenti, Wheat Ridge, CO, USA Behnaz Jafari, Athens, OH, USA Taejin Jang, Seattle, WA, USA Tanner Jankins, Boston, MA, USA Sarah Jessl, Cambridge, Cambridgeshire, United Kingdom Abby Jones, Storrs, CT, USA Daniel Juarez-Robles, College Station, TX, USA Roland Jung, Munich, BY, Germany Xiangyi Ke, Houston, TX, USA

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

NE W MEMBERS Yi-Yun Ke, Hsinchu, Taiwan, Taiwan Jonas Keil, Muenchen, BY, Germany Peter Keil, Muenchen, BY, Germany Taylor Kelly, Houston, TX, USA Frank Kindermann, Muenchen, BY, Germany Jeroen Kint, Gent Oost-Vlaanderen, Belgium Simone Koecher, Muenchen, BY, Germany Suresh Konda, Thunder Bay, ON, Canada Stephan Kosch, Munchen, BY, Germany Muthu Krishna, University Road, Hampshire, United Kingdom Tonni Kurniawan, Sapporo, Sapporo, Japan Chun-Han Lai, Los Angeles, CA, USA Rachel Langenbacher, New York, NY, USA Daniela Ledwoch, Oxford, Great Britian Ching-Feng Lee, Tao-Yuan, Taiwan, Taiwan Eunji Lee, Auburn, AL, USA Jialang Li, Calgary, AB, Canada Jianyu Li, Austin, TX, USA Jingkun Li, Malden, MA, USA Lu Li, Troy, NY, USA Szu-Ying Li, Hsinchu, Taiwan, Taiwan Wangda Li, Austin, TX, USA Yanhong Li, Austin, TX, USA Ying-Chun Li, Hsinchu, Taiwan Yu-Lun Liang, Los Angeles, CA, USA Jose Lorie Lopez, Columbus, OH, USA Hamid Reza Lotfi Zadeh Zhad, Lincoln, NE, USA James Lowe, Fayetteville, AR, USA Fang-Chun Lu, Taipei, Taiwan, Taiwan Liu Luo, Austin, TX, USA Yuxi Ma, East Lansing, MI, USA Angela Macedo Andrade, Fresno, CA, USA Laura Maggini, Cambridge, Cambridgeshire, United Kingdom Pratiti Mandal, Pittsburgh, PA, USA Luca Mastropasqua, Milan Milan, Italy John Matthiesen, Ames, IA, USA Josefine McBrayer, Albuquerque, NM, USA Melissa McCarthy, Cork, Ireland Adan Medina, Pullman, WA, USA Hamed Mehrabi, Fayetteville, AR, USA Hemma Mistry, St Petersburg, FL, USA Abdelrhman Mohamed, Pullman, WA, USA Chandra Mohan, Gurgaon, India Animesh Mondal, Auburn, AL, USA Guo Sheng James Moo, Singapore, Singapore Sromana Mukhopadhyay, Kearny, NJ, USA

Sanjay Nanda, Austin, TX, USA Adriana Navarro-Suarez, Minano Menor Araba, SPAIN Bertrand Neyhouse, Athens, OH, USA Aaron Nicholson, Fayetteville, AR, USA William Odette, Montreal, Canada Moses Oguntoye, New Orleans, LA, USA Arnau Oliva Puigdomenech, Gent Flandes, Belgium Chinomso Onuoha, bozeman, MT, USA David Ortega, Queretaro, Querétaro, Mexico Benjamin Ossonon, Montreal, QC, Canada Tejkiran P J, Puttaparthi Andhra Pradesh, India Benjamin Papandrea, Los Angeles, CA, USA Min Je Park, Austin, TX, USA Werner Paschinger, Vienna, W, Austria Syed Pasha, Miami, FL, USA Zoran Pavlovic, Muelheiman der Ruhr, Germany Lorenzo Pedrazzetti, Soncino, Italy Isaias Peraza, Mesa, AZ, USA Dan Petrescu, Montreal, QC, Canada Robert Pipes, Austin, TX, USA Spencer Porter, Piscataway, NJ, USA Daniel Pritzl, Garching, BY, Germany Geer Qile, Victoria, BC, Canada Yiheng Qin, Hamilton, ON, Canada Diego Fernando Quintero Pulido, Amersfoort Utrecht, Netherlands Sahithya Reddivari, Ann Arbor, MI, USA Abiral Regmi, Hsinchu Hsinchu City, Taiwan Lena Reichenbach, Liverpool, Merseyside, United Kingdom Lorlyn Reidy, Oxford, MS, USA Alexander Rheinfeld, Munich, BY, Germany Bernhard Rieger, Muenchen, BY, Germany Daniel Roxbury, New York, NY, USA Katharina Rumpf, Muenchen, BY, Germany Karan Sahni, Chicago, IL, USA Laurence Savignac, Longueuil, Canada Zebulon Schcihtl, Fayetteville, AR, USA Markus Schuderer, Garching, BY, Germany Joerg Schuster, Muenchen, BY, Germany Rollin Scott, Tallahassee, FL, USA Yosi Shamay, New York, NY, USA Hamed Shamkhalichenar, Baton Rouge, LA, USA Wenqian Shan, Houston, TX, USA Pei Sian Shao, Taoyuan City, Taiwan, Taiwan

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

Alon Shapira, Haifa, Israel Asma Sharafi, Ann Arbor, MI, USA Chen Sheng, Tao-Yuan, Taiwan, Taiwan Young Ho Shin, Baton Rouge, LA, USA Mahander Singh, Bangalore, KA, India Hunter Sismaet, Boston, MA, USA Giji Skaria, Orlando, FL, USA Pedro Sobrinho, Fortaleza, Ceara, Brazil Bohang Song, Austin, TX, USA Franz Spingler, Muenchen, BY, Germany Chhayly Sreng, Phnom Penh Phnom Penh, Cambodia Lisa Stephens, Montreal, QC, Canada HoHyun Sun, Austin, TX, USA Shu Min Tan, Singapore, Singapore Rou Jun Toh, Singapore, Singapore Anh Phong Tran, Somerville, MA, USA Ping-Hsin Tsai, Taipei, Taiwan, Taiwan Marianna Uceda, Montreal, QC, Canada Vasileia Vogiazi, Cincinnati, OH, USA Walter Wakem, Sherbrooke, QC, Canada Johannes Wandt, Garching, BY, Germany Hong Wang, Singapore, Singapore Jian Wang, Hong Kong, Hong Kong Pin Wang, Taoyuan, Taiwan, Taiwan Shen Wang, La Jolla, CA, USA Joern Wilhelm, Muenchen, BY, Germany Cody Wilkins, Aiken, SC, USA Ryan Williams, New York, NY, USA Hope Wilson, Austin, TX, USA Shang-Jung, Wu, Lausanne, VD, Switzerland Thomas Wynn, Oceanside, CA, USA Qiang Xie, Austin, TX, USA Xing Xing, San Diego, CA, USA Jiagang Xu, Lexington, KY, USA Lu Yang, San Diego, CA, USA Gamze Yilmaz, Singapore, Singapore Chen Ying, Gainesville, FL, USA Or Yosef, Beer Sheva, Israel Chengjun YU, Heverlee, Belgium Fangping Yuan, Rolla, MO, USA Vishal Zade, Merced, CA, USA Nicholas Zaibaq, Houston, TX, USA Stanislaw Zankowski, Leuven, Belgium Nan Zhang, Morgantown, WV, USA Meng Zhao, Cleveland, OH, USA Yuntong Zhu, Atlanta, GA, USA Feng Zou, Akron, OH, USA Vitalijs Zubkovs, Lausanne, VD, Switzerland

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NE W MEMBERS Member Anniversaries It is with great pleasure that we recognize the following ECS members who have reached their 30, 40, 50, and 60 year anniversaries with the society in 2016. Congratulations to you all!

60 Years

40 Years

30 Years

Robert P. Frankenthal C.G.A. Hill Kurt H. Stern Gerald C. Whitnack

Madhav Datta Gilbert Declerck Karl W. Frese Richard D. Goodin James S. Harris William R. Heineman Theodore I. Kamins Martin W. Kendig Donald W. Kirk Jiri Klinger Tyler X. Mahy Kimon Papadopoulos Patricia Paulette James B. Pierce Ronald A. Rizzo Rajendra Singh Subhash C. Singhal Lawrence A. Tinker Georg Wahl John P. Willis Masamichi Yamashita Jose H. Zagal

Jennifer A. Bardwell J.M. Bastidas Christopher M.A. Brett Gessie Brisard Arturo Bronson Steve Crouch-Baker Ronald A. Dombro Jeff Gambino David Genders Milton Neal Golovin Domingo Gonzalez-Arjona Arnold Z. Gordon Shimshon Gottesfeld Michael John Graham Steven G. Greenbaum Hans Aage Hjuler Michael A Kepros Signe Kjelstrup Rodney M. Lafollette Keryn K. Lian

50 Years Herbert D. Barber David W. Boone David James Curran Arabinda N. Dey Michael Gulla William G. Howard Marshall J. Kidder Dieter Landolt Frederick Leon Marsh Herbert J Moltzan Boone B. Owens R. Winston Revie Geraldine Cogin Schwartz

Bor Yann Liaw Philippe Marcus James B. McMahon Norio Miura Tasuo Nakato Gholam-Abas Nazri Lori Nye David Ofer Isabel Pereira Allen R. Powers Shi-Woo Rhee Ravindra V. Shenoy Toshio Shibata Karl E. Spear Joseph Stockel W. Stephen Tait Francisco A. Uribe Petr Vanýsek Masataka Wakihara John Weidner Andrzej Wieckowski Chester V. Zabielski

SOFC-XV

15th International Symposium on Solid Oxide Fuel Cells :

Hollywood, Florida, USA July 23-28, 2017 Subhash C. Singhal Pacific Northwest National Lab. Richland, WA, USA

The Electrochemical Society SOFC Society of Japan

Sponsors

CHAIRS

Diplomat Resort & Spa

Save the Date Tatsuya Kawada Tohoku University Sendai, Japan

www.electrochem.org/sofc-xv

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The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

STUD

NE W MEMBERS

T N IO E T

You may be eligible for a

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Awarded Student Membership

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QUESTIONS? Contact Membership Services The Electrochemical Society Interface • Summer 2016 • www.electrochem.org at customerservice@electrochem.org for more information.

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t ST ech UDENT highligh NE WS ts

Student Chapter News Auburn University Student Chapter The ECS Auburn University chapter was founded in 2007. It has a multidisciplinary group of inquisitive student members from materials engineering, chemical engineering, and the chemistry and physics department. They are a thriving organization with a team of 18 active students, which ranked among the top 10 academic institutions by student ECS membership this year.

Under the leadership of the student officers and faculty advisor Majid Beidaghi, Assistant Professor in Materials Engineering, the chapter has put together seven meetings for “lunch and learn” sessions. These sessions allowed students to present their research in an informal environment. Nine students presented their research on topics such as photoelectrochemisty for hydrogen production, electrochemical sensors, and bio-fuel cells to 2D nano-materials for supercapacitors. These sessions not only enhanced interdisciplinary learning but also provided opportunities for collaborative research.

We observed remarkable attendance during these meetings. The chapter also organized a poster presentation competition on December 3, 2015 to promote The Electrochemical Society and recognize the ongoing research in the field of electrochemistry and solid state science at Auburn University. The top three presentations were selected and awarded by a panel of judges. These sessions cultivated a convivial atmosphere conducive to academic conversation.

This summer Auburn University’s student chapter is planning an oral presentation competition, a special faculty seminar, and a variety of other activities. For more details about our chapter, please visit and like our Facebook page at www.facebook.com/ECSatAU.

Yoonsung Chung presented her research during a “lunch and learn” session.

Hossein Talebinezhad (right) presented his poster to judge Jin Wang (left) at the poster competition.

Animesh Mondal (second from right), one of the three winners of the poster competition, with three of the judges (left to right) Majid Beidaghi, Jeffrey Fergus, and Jin Wang.

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The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

t ST ech UDENT highligh NE WS ts Drexel University Student Chapter On April 28, 2016, the Drexel University Student Chapter hosted the 1st Philadelphia Electrochemical Society Symposium, which attracted over 50 participants from Rowan University, University of Pennsylvania, Temple University, and Drexel University.. Keynote speaker, Beth Fisher, Director of Membership Services at ECS, opened the symposium and talked about the many opportunities ECS offers through publications, outreach, and conferences. Short presentations were then given by attendees showing how electrochemistry was used in their research. Presenters included Maureen Tang (Drexel), Eric Borguet (Temple), Michael Edley (Drexel), Cecilia Tommos (UPenn), Bryan Byles (Drexel), Katherine Willets (Temple), Lei Yu (Rowan), Paramesawara Chinnam (Temple), Bilen Akuzum

(Drexel), Caitlin Dillard (Drexel), and Katie Van Aken (Drexel). The afternoon included a poster session, which inspired conversation and partnership among the students. From batteries to supercapacitors, solar cells to flowable energy storage devices, ionic liquids to solid electrolytes, optical microscopy to advanced characterization, there was something for everyone to enjoy.

Current ECS Philadelphia Chapter board members include: Muhammad Boota, president; Bryan Byles, vice President; Mallory Clites, secretary; Kathleen Maleski, treasurer; Patrick Urbankowski, librarian; and Ekaterina Pomerantseva, faculty advisory. With success in the debut year, the Philadelphia ECS Symposium is expected to return as an annual event.

Attendees of the 1st Philadelphia Electrochemical Society Symposium included faculty and students from Drexel University, Temple University, University of Pennsylvania, and Rowan University.

University of Kentucky Student Chapter M. Stanley Whittingham from the State University of New York at Binghamton was the guest of the ECS Kentucky Student Chapter and the department of Chemical and Materials Engineering at the University of Kentucky. Dr. Whittingham visited the campus in April 2016 and gave a seminar on “The Ultimate Limits of Intercalation Reactions of Li-Batteries.”

He met with the graduate students, discussed current issues in energy storage systems, and provided them with career advice. Dr. Whittingham’s seminar was a campus-wide event, and was attended by faculties and students from both College of Engineering and College of Arts & Sciences at the University of Kentucky.

Pictured left to right are: Xiaowen Zhan, current chair of the Kentucky Student Chapter; M. Stanley Whittingham; Syed Islam; Jie Pan, former Chair of Kentucky Student Chapter; Shuang Gao; and Mona Shirpour, faculty advisor of the Kentucky Student Chapter.

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

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ECS STUDENT PROGRAMS

Awarded Student Membership Summer Fellowships

ECS Divisions offer Awarded Student Memberships to qualified full-time students.

To be eligible, students must be in their final two years of an undergraduate program or enrolled in a graduate program in science, engineering, or education (with a science or engineering degree). Postdoc students are not eligible.

Memberships include generous meeting discounts, an article pack with access to the ECS Digital Library, a subscription to Interface, and much more. uApply www.electrochem.org/student-center uQuestions customerservice@electrochem.org uDeadline Renewable yearly

The ECS Summer Fellowships were established in 1928 to assist students during the summer months.

Travel Grants Several of the Society’s divisions and sections offer Travel Grants to students, postdoctoral researchers, and young professionals presenting papers at ECS meetings.

Please be sure to review travel grant requirements for each division and sections. In order to apply for a travel grant, formal abstract submission is required for the respective meeting you wish to attend. uApply www.electrochem.org/travel-grants

The next round of fellowships will be presented in 2017.

Please visit the ECS website for complete rules and nomination requirements.

uApply www.electrochem.org/fellowships uQuestions awards@electrochem.org uDeadline January 15, 2017

uQuestions travelgrant@electrochem.org

uNote Applicants must reapply each year

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t ST ech UDENT highligh NE WS ts University of Maryland Student Chapter On Friday, April 8, 2016, the UMD Student Chapter held officer elections during a regular meeting of the chapter. Patrick Stanley, previously Treasurer, was elected President; Steven Lacey was elected Vice President; Mann Sakbodin was elected Treasurer; and Alireza Pesaran was voted to remain as Secretary. While there was a

good degree of turnover in the officers due to upcoming graduations, the elections were held early enough to ensure a smooth transition with sufficient overlap between current and past officers.

Student Chapter Munich The recently founded ECS Student Chapter Munich (ECS SCM, approved October 15, 2015) has been already quite busy. It hosted its first workshop on October 22, 2015, and introduced bi-weekly ECS SCM Journal Club sessions beginning in January 2016.

However, so far the highest impact activity was the 1st ECS SCM Symposium, which was held on February 15, 2016. Not only did the

72 participants share their findings during the poster session, but also two invited speakers, Jeff Dahn (Dalhousie University) and Thomas Schmidt (Paul-Scherrer-Institute), highly involved members within the ECS and researchers of remarkable scientific impact, presented their recent findings at this event.

Jeff Dahn during his presentation, “It is hard to make a Li-ion battery last a long time, but even harder to prove that it will,” at the 1st ECS Student Chapter Munich Symposium.

Thomas Schmidt during his presentation, “Oxygen Evolution on Non-Noble Metal Catalysts,” at the 1st ECS Student Chapter Munich Symposium.

A group picture with the attendees of the 1st ECS Student Chapter Munich Symposium at the entrance of the TUM IAS building on February 15, 2016.

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t ST ech UDENT highligh NE WS ts Ohio University Student Chapter On Friday, April 8, 2016, the Ohio University ECS Student Chapter visited the Ohio Valley Museum of Discovery in Athens, and took part in an educational demonstration and presentation for young children and their parents on urea electrolysis. This was in the late morning on April 16. Gerardine Botte, director of the CEER at OU, gave a presentation on its urea electrolysis technology that the ECS student chapter then demonstrated to the children present. The demonstration

was based on a presentation already shown at the STEM perspective student outreach.

ECS IE&EE Division members Gerardine Botte and Madhivanan Muthuvel, and OU ECS student chapter secretary Ben Sheets conducted the presentation and demonstration. The event was hosted by the Ohio Valley Museum of Discovery and attended by several young children, most of whom were of elementary school age, with many of their parents participating as well.

Research Triangle Student Chapter In September 2015, the Research Triangle Student Chapter, along with the local Materials Research Society (MRS) student chapters, hosted the annual Triangle Student Research Competition. The event included 56 posters from students at Duke University, North Carolina State University, and the University of North Carolina showcasing their research. Chapter members James Thostenson, Jonathan Boltersdorf, Seokhyoung Kim, and Ishan Joshipura received a certificate for their excellent contribution.

In collaboration with Pine Research Instrumentation, the chapter hosted their spring social in February 2016. Pine Research Instruments provided an informative presentation on how to get a job in industry with excellent views from newly hired graduates, seasoned scientists, and managers. Everyone had a great night of food, drink, and networking with local colleagues.

Research Triangle ECS Student Chapter along with Pine Research Instruments during the 2016 Spring Kickoff Evening Social (from left): Kevin Olson (UNC), Marion Jones (Pine Research Instrumentation), Christine Kim (Duke), Alex Peroff (Pine), Leslie Wilson (NCSU), James Daubert (NCSU), Frank Dalton (Pine Research Instrumentation), Martin Dufficy (NCSU), and Timothy Paschkewitz (Pine Research Instrumentation).

?

Did You

Know

As the student chapter roster continues to expand within ECS, did you know that our chapters can form as a campus-based model or as a regional-based model? What is the difference? Campus-based chapters exist at a specific academic institution (e.g., University of California, San Diego) while regional-based chapters exist between multiple academic institutions within that region (e.g., Research Triangle has active participation of students from University of North Carolina-Chapel Hill, Duke University, and North Carolina State University).

Do you want to start a chapter but are not sure which model best fits your prospective chapter?

Contact Beth Fisher, Director of Membership Services, at beth.fisher@electrochem.org for assistance.

72

The Electrochemical Society Interface â&#x20AC;˘ Summer 2016 â&#x20AC;˘ www.electrochem.org

t ST ech UDENT highligh NE WS ts United Kingdom North West Student Chapter The inaugural UK North West Student chapter symposium took place in Manchester, England on February 10, 2016. There was an amazing turnout made up of members from the chapter, lecturers from Manchester, Liverpool and Chester, and non-member postgraduates.

The afternoon started with a fantastic talk from Patrick Unwin from the University of Warwick titled “Nanoscale Views of Interfacial Flux Processes: From Electrodes to Living Cells.” His lecture introduced some of the techniques optimized by his research group to study chemical fluxes directly at key features of the electrode surfaces, such as steps, terraces and grain boundaries.

The second speaker, John Griffin from Lancaster, delivered a talk titled “Understanding Supercapacitor Charging Mechanisms using NMR Spectroscopy,” on the use of NMR as a tool for electrochemistry, with a focus on ionic liquids supercapacitors. A poster session was the best way to conclude an already great afternoon. Everyone that presented a poster received an engaging scientific discussion, and the student chapter achieved their goal, in providing a platform for students to network and receive feedback on their current research.

University of Virginia Student Chapter University of Virginia Student Chapter continued the tradition of successful seminar series by hosting Jim Moran from the Navy Research Lab on February 18, 2016. His presentation titled “Corrosion Engineering in the Industrial World” gave an insight into the application of electrochemistry to solve real world problems. Dr. Moran, a University of Virginia alumnus, showed various examples from his career spanning over 25+ years showcasing the use of scientific knowledge to solve industrial problems. The audience, consisting of mostly graduate students, was fascinated to see what awaits them when they leave the hallowed halls of the Center of Electrochemical Science and Engineering (CESE).

More recently the chapter organized a second seminar with guest speaker Jeffrey Glass from Duke University on April 8, 2016. Dr. Glass presented a seminar highlighting his work on graphenated carbon nanotubes in electrode applications. Dr. Glass’s presentation on the issues and challenges encountered in the deposition and

characterization of carbon nanotubes sparked great interest. The chapter was fortunate to leverage Dr. Glass's expertise as the Faculty Director of the Pratt School’s Master of Engineering Management Program at Duke University and followed the technical seminar with an interactive talk and discussion on “Top 10 mistakes early career professionals make in the real world.” This professional career development seminar was very well received by graduate students and gave an insight into available career paths and how to choose the best fit after graduation.

Both seminars were well received by and brought together students and faculty from various departments such as Chemistry, Chemical Engineering, Electrical and Computer Engineering, and Materials Science and Engineering. Students and faculty also had the opportunity to meet with both speakers and have engaging discussion prior to and after their respective seminars, which initiated possible collaborations.

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2015 Y e a r in REMembers vie w ECS Institutional The Electrochemical Society values the support of our institutional members. Institutional members help ECS support scientific education, sustainability and innovation. Through ongoing partnership, ECS will continue to lead as the advocate, guardian, and facilitator of electrochemical and solid state science and technology.

Visionary

AMETEK – Scientific Instruments (35) USA

Metrohm USA (10) USA

Benefactor Asahi Kasei Corporation (8) Japan BASi (1) USA Bio-Logic USA (8) USA Duracell (59) USA Gamry Instruments (9) USA Gelest Inc. (7) USA

Hydro-Québec (9) Canada Industrie De Nora S.p.A. (33) Italy Pine Research Instrumentation (10) USA Saft Batteries, Specialty Battery Group (34) USA Scribner Associates Inc. (20) USA Zahner-elektrik (1) Germany

Patron El-Cell (2) Germany Energizer (71) USA Faraday Technology, Inc. (10) USA IBM Corporation (59) USA

Lawrence Berkeley National Lab (12) USA Panasonic Corporation (22) Japan Toyota Research Institute of North America (8) USA

Sponsoring Axiall Corporation (21) USA Central Electrochemical Research Institute (23) India Electrosynthesis Company, Inc. (20) USA Ford Motor Company (2) USA GS-Yuasa International Ltd. (36) Japan Honda R&D Co., Ltd. (9) Japan IMERYS Graphite & Carbon (29) Switzerland Medtronic, Inc. (36) USA Molecular Rebar Design (1) USA Next Energy EWE – Forschungzentrum (8) Germany

Nissan Motor Co., Ltd. (9) Japan Permascand AB (13) Sweden TDK Corporation, Device Development Center (23) Japan Technic, Inc. (20) USA Teledyne Energy Systems, Inc. (17) USA Tianjin Battery Joint-Stock Co., Ltd (2) China Toyota Central R&D Labs., Inc. (36) Japan Yeager Center for Electrochemical Sciences (18) USA ZSW (12) Germany

Sustaining 3M Company (27) USA General Motors Research Laboratories (64) USA Giner, Inc./GES (30) USA International Lead Zinc Research Organization (37) USA Kanto Chemical Co., Inc., (4) Japan Leclanche SA (31) Switzerland

Los Alamos National Laboratory (8) USA Occidental Chemical Corporation (74) USA Quallion, LLC (16) USA Sandia National Labs (40) USA SanDisk (2) Japan Western Digital (1) USA

Please help us continue the vital work of ECS by joining as an institutional member today. To join or discuss institutional membership options please The Electrochemical Society Interface • Summer 2016 • www.electrochem.org ext. 103 or beth.fisher@electrochem.org.

74 contact Beth Fisher, Director of Membership Services at 609.737.1902 (Number in parentheses indicates years of membership)

03/21/2016

2015 Y e a r in Re vie w Note: The 2015 ECS Annual Report has been published as a supplement to this issue of Interface. Additional information is presented on the following pages as the 2015 Year in Review.

ECS Board of Directors

(as of October 31, 2015)

Officers

ECS Staff

Daniel Scherson, President Frank Hovorka Professor of Chemistry Director, Ernest Yeager Center for Electrochemical Sciences Case Western Reserve University

Dinia Agrawala, Graphic Designer/Interface Production Manager

Krishnan Rajeshwar, Sr. Vice President Distinguished Professor Interim Associate VP for Research University of Texas Arlington

Linda Cannon, Staff Accountant

Johna Leddy, 2 Vice President Associate Professor The University of Iowa

Karla Cosgriff, Director of Development

nd

Yue Kuo, 3rd Vice President Dow Professor Texas A&M University Hariklia Deligianni, Secretary Smarter Planet Initiatives IBM E. Jennings Taylor, Treasurer Chief Technical Officer Intellectual Property Director Faraday Technology, Inc. Roque J. Calvo, Executive Director Chief Executive Officer The Electrochemical Society

Directors

Marcelle Austin, Board Relations Specialist Roque J. Calvo, Executive Director/Chief Executive Officer Karen Chmielewski, Finance Associate Paul B. Cooper, Editorial Manager Tammi Doerfler, Human Resources & Operations Manager Casey Emilius, Meetings Specialist Beth Fisher, Director of Membership Services Tim Gamberzky, Chief Operating Officer Rob Gerth, Director of Marketing & Communications Annie Goedkoop, Director of Publications Production Paul Grote, Director of Finance Andrea L. Guenzel, Publications Specialist Mary Hojlo, Membership & Constituent Services Specialist Christie Knef, Director of Meetings John Lewis, Associate Director of Meetings Winnie Mutch, Web Manager Anna Olsen, Senior Content Associate & Library Liason Beth Schademann, Publications Specialist

Scott Calabrese Barton, Chair, Energy Technology Division

Amanda Staller, Web Content Specialist

Mekki Bayachou, Chair, Organic & Bio. Electrochemistry Div.

Logan Streu, Content Discoverability Specialist

Rudolph Buchheit, Chair, Corrosion Division

Beth Anne Stuebe, Meetings Content Manager

Bryan Chin, Chair, Sensor Division

Mary E. Yess, Deputy Executive Director & Chief Content Officer

Turgut Gür, Chair, High Temperature Materials Division Paul Kohl, Past President Robert Kostecki, Chair, Battery Division Pawel Kulesza, Chair, Physical & Analytical Electrochemistry Div. Dolf Landheer, Chair, Dielectric Science & Technology Div. Mark Overberg, Chair, Electronics & Photonics Division Elizabeth Podlaha-Murphy, Chair, Electrodeposition Division Madis Raukas, Chair, Luminescence & Display Materials Div. Venkat Subramanian, Chair, Indust. & Electrochem. Eng, Div. Stuart Swirson, Nonprofit Financial Professional Eric Wachsman, Chair, Interdisciplinary Sci. & Tech. Subcommittee R. Bruce Weisman, Chair, Nanocarbons Division

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2015 Y e a r in RE vie w

ECS Membership Statistics Category

Table I. ECS Membership by Class 2010 2011 2012

Active-Good Standing* 4861 4731 Active-Expired* Active-Lapsed* Member Representative-Good Standing* 113 112 Member Representative-Expired* Member Representative-Lapsed* Life 49 52 Emeritus 280 289 Honorary 23 23 Subtotal Active in Good Standing* 5326 5207 Total Active Delinquent (Expired + Lapsed)* 1208 1236 Total Active 6534 6443 Student-Good Standing* 1509 1427 Student-Expired* Student-Lapsed* Total Student Delinquent (Expired + Lapsed)* 710 825 Total Students 2219 2252 Total Individual Members 8753 8695 *Number represents a refocus in the categorization of good standing, expired & lapsed members.

Section (good standing)

Division (good standing)

2014

2015

2015/2014 # Change

2015/2014 % Change

4657

4253

4260

134

175

219

64 288 22 5165 1302 6467 1502

101 283 25 4837 1225 6062 1438

105 296 27 4907 1143 6050 1497

847 2349 8816

775 2213 8275

760 2257 8307

3889 393 1235 269 16 10 117 299 22 4596 1654 6250 1519 228 858 1086 2605 8855

-371 393 1235 50 16 10 12 3 -5 -311 511 200 22 228 858 326 348 548

-8.71 0.00 0.00 22.83 0.00 0.00 11.43 1.01 -18.52 -6.34 44.71 3.31 1.47 0.00 0.00 42.89 15.42 6.60

2013

2014**

2015*

2015/2013 # Change

2015/2013 % Change

109 65 381 182

98 102 N/A 66 47 N/A 382 371 N/A 180 155 N/A 10 13 N/A 86 78 N/A 124 106 N/A 116 96 N/A 1108 1041 N/A 179 133 N/A 59 59 N/A 39 27 N/A 775 756 N/A 253 205 N/A 30 30 N/A 154 162 N/A 360 292 N/A 80 58 N/A 416 376 N/A 123 87 N/A 146 142 N/A 76 53 N/A **2014 section statistics are not available.

89 27 256 215 7 64 74 94 1005 136 70 31 636 146 49 147 217 66 244 64 122 47

-13 -20 -115 60 -6 -14 -32 -2 -36 3 11 4 -120 -59 19 -15 -75 8 -132 -23 -20 -6

-12.75 -42.55 -31.00 38.71 -46.15 -17.95 -30.19 -2.08 -3.46 2.26 18.64 14.81 -15.87 -28.78 63.33 -9.26 -25.68 13.79 -35.11 -26.44 -14.08 -11.32

81 123 118 1105 171 58 39 771 243 31 159 381 87 413 122 144 74

Table III. ECS Membership by Division 2010 2011 2012

Battery 1534 Corrosion 482 Dielectric Science & Technology 320 Electrodeposition 463 Electronics & Phontonics 687 Energy Technology 1155 Nanocarbons Division 190 High Temperature Materials 207 Industrial Electrochemistry & Electrochemical 302 Eng Luminescence & Display Materials 107 Organic & Biological Electrochemistry 204 Physical & Analytical Electrochemistry 640 Sensor 225 Total 6516 *2015 does not include expired members prior to termination.

Occupation

2013

Table II. ECS Membership by Section 2010 2011 2012

Arizona 127 Brazil 65 Canada 380 Chicago 159 Chile China 101 Cleveland 125 Detroit 98 Europe 1256 Georgia 165 India Israel 31 Japan 791 Korea 262 Mexico 36 National Capital 159 New England 291 Pittsburgh 87 San Francisco 415 Taiwan 97 Texas 160 Twin Cities 86 *2015 does not include expired members prior to termination.

(as of October 1, 2015)

2013

2014

2015*

2015/2014 # Change

2015/2014 % Change

-123 -8 -31 -53 -45 -30 -23 16

-6.74 -1.84 -13.19 -11.91 -8.09 -2.93 -12.99 7.92

1668 456 319 483 679 1220 176 184

1709 427 275 448 550 1194 160 218

1987 458 256 464 581 1122 183 212

1824 434 235 445 556 1025 177 202

1701 426 204 392 511 995 154 218

307

290

303

282

286

4

1.42

111 184 618 229 6634

97 176 564 217 6325

94 180 609 233 6682

90 166 561 218 6215

64 161 560 225 5897

-26 -5 -1 7 -318

-28.89 -3.01 -0.18 3.21 -5.12

Table IV. ECS Membership by Occupation (active in good standing) 2010 2011 2012 2013 2434 2094 387 109

2362 2123 377 110

2206 1902 377 111

2014

2015*

2015/2014 # Change

2015/2014 % Change

5024

4972

4596

4798

Academic 2517 Industry 2005 Government 386 Retired 114 Other Total 5022 *2015 does not include expired members prior to termination.

76

2346 1900 435 117

2227 1724 360 119 121 4551

-119 -176 -75 2 121 -247

-5.07 -9.26 -17.24 1.71 0.00 -5.15

The Electrochemical Society Interface â&#x20AC;˘ Summer 2016 â&#x20AC;˘ www.electrochem.org

2015 Y e a r in Re vie w

Finance We are pleased to present the audited financial statements of ECS for the year ended December 31, 2015. These reports indicate that our financial health continues to be strong in spite of a decrease in the market value of our investment portfolio and that we continue to work toward the Society’s objectives of contributing to the advancement of electrochemical and solid state science through the dissemination of technical content.

For the year ended December 31, 2015, net assets decreased by $367,097. The deficit was a result of revenues, which were less than budget, totaling $6.9 million, and expenses of $7.3 million. The revenue budget shortfall was largely due to decreases in the market value of securities in the investment portfolio of $0.5 million.

This was partially offset by greater than expected performance in publications and meetings areas.

The total operating expenses increased to $7.3 million primarily due to increased publications, general and administrative, fundraising, and marketing costs compared to the previous year.

Marketing, and general and administrative costs increased due to important upgrades to the customer relations database and ECS Website.

The Society’s Statement of Financial Position reflects assets of $16.5 million. Of these total assets, 68.1% are either custodial or endowment funds. Growth in these funds is important because it is clear that there will be pressure to generate financial support through investment and contribution revenues. The Free the Science open access initiative has shifted our focus to the eventual free dissemination of content. Digital Library subscription prices have been frozen and, over time, will begin to decline as we shift from a subscription-based model to a contribution-based model. Our broader financial goal is to avoid the use of the endowment funds to cover operating expenses, if possible, enabling the funds to maintain future growth.

From an operational perspective, 2015 was a good year for ECS, largely due to the strong attendance at our biannual and satellite meetings. However, the investment portfolio did not perform as it has over the past several years. We anticipate the continued need for significant investments to fund the technology necessary to advance our programs, disseminate content and support the open access initiative. The Society’s current financial strength will aid in these investments.

E. Jennings Taylor Treasurer

Tim Gamberzky Chief Operating Officer

The Electrochemical Society is a nonprofit international association of scientists and engineers chartered as a tax-exempt organization under Section 501(c) (3) of the United States Internal Revenue Code. The Board of Directors engages the services of an independent auditor to assure that the Society maintains an effective system of financial management, and operates under its nonprofit charter. The Board of Directors received an unmodified or clean opinion from their independent auditors, WithumSmith+Brown for the fiscal year ending December 31, 2015.

To obtain a complete copy of the Audit Financial Statements, interested parties can e-mail their request to paul.grote@electrochem.org.

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2015 Y e a r in RE vie w

Financial Summary Consolidated Statement of Financial Position (For the years ended December 31, 2015 and 2014)

Assets

Cash and cash equivalents Accounts receivable, net Unconditional promises to give, net Prepaid expenses, deposits and other assets Investments in marketable securities Custodial account investments Deferred rent Investments in real estate: Land Buildings, less accumulated depreciation of $773,127 and $688,163 in 2015 and 2014, respectively.

Total assets

Liabilities and Net Assets

Liabilities Accounts payable and accrued expenses Deferred revenue Custodial account liability Security deposits Deferred compensation Net Assets Unrestricted Temporarily restricted Permanently restricted Total net assets Total liabilities and net assets

2015

2014

1,603,427 2,631,057 $16,496,345

1,603,427 2,716,021 $16,906,236

$344,305 1,432,147 83,059 39,391 134,571

$335,696 1,396,767 161,891 37,141 144,772

13,092,002 469,802 901,068 14,462,872 $16,496,345

13,445,911 491,190 892,868 14,829,969 $16,906,236

$2,636,802 643,650 25,165 2,844,332 298,902 127,918 345,346 516,324 264 7,438,703

$2,726,619 641,975 80,569 2,199,348 1,122,986 74,631 295,975 505,819 12,374 7,660,296

$2,401,337 300,732 70,950 2,228,543 300,000 219,208 5,520,770

$2,214,212 322,145 200,126 2,349,033 245,282 169,269 5,500,067

408,836 626,740 189,588 566,249 1,791,413 7,312,183 126,520 (493,617) (367,097) 14,829,969 $14,462,872

945,150

$805,208 35,396 18,585 95,418 11,158,854 83,059 65,341

$864,867 4,568 19,385 131,377 11,341,707 161,891 62,993

Consolidated Statement of Changes in Net Assets (For the years ended December 31, 2015 and 2014)

Revenues

Publications Membership Constituent programs Society meetings and activities Investment income Contributions Grants Rental income Other revenues Total Revenues

Expenses

Program services Publications Membership Constituent programs Society meetings and activities Grant sub-awards Awards, fellowships and grants Total Program Services Expenses Supporting services General and administrative Marketing Fundraising Rental operations Total Supporting Services Expenses Total Expenses Increase in net assets from operations Net change in fair value of investments Change in net assets Net assets, beginning of year Net assets, end of year

102,123 575,950 1,623,223 7,123,290 537,006 117,916 654,922 14,175,047 $14,829,969

These financial statements are a condensed version of the audited statements of ECS for the years ended December 31, 2015 and 2014. ECS will be pleased to provide complete copies along with all footnotes and the unqualified report of our auditors upon request.

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2015 Y e a r in Re vie w

Notes to Financial Statements 1. Summary of Significant Accounting Policies

4. Endowment Funds

The consolidated financial statements include the accounts of The Electrochemical Society, Inc. (the Society) and its Divisions, Groups and Sections and ECS Holdings, LLC, (the LLC). All intercompany balances and transactions have been eliminated in consolidation. The consolidated financial statements are prepared on the accrual basis of accounting. Revenue, other than contributions, is recognized when earned and expense is recognized when the obligation is incurred.

The consolidated financial statements have been prepared to focus on the Society and its subsidiaries as a whole, and to present balances and transactions according to the existence or absence of donor-imposed restrictions. Accordingly, net assets and changes therein are classified as follows: Unrestricted net assets – net assets not subject to donor-imposed stipulations; Temporarily restricted net assets – net assets subject to donor-imposed stipulations that will be met by actions of the Society and/or by the passage of time; Permanently restricted net assets (endowment funds) – net assets subject to donor-imposed stipulations that they be maintained permanently by the Society.

The Society’s endowment funds consist of several funds established to fund awards, as well as an educational endowment fund and a Free the Science fund. The endowment funds include both donor-restricted funds and funds designated by the Board of Directors to function as endowments. As required by generally accepted accounting principles (GAAP), net assets associated with endowment funds are classified based on the existence or absence of donor-imposed restrictions.

The Society’s policy requires the preservation of the fair value of the original gift as of the gift date of the donor-restricted endowment funds absent explicit donor stipulations to the contrary. As a result, the Society classifies as permanently restricted net assets the original value of gifts donated to the permanent endowment and the original value of subsequent gifts to the permanent endowment.

The remaining portion of the donor-restricted endowment fund that is not classified in permanently restricted net assets is classified as temporarily restricted net assets until those amounts are appropriated for expenditure by the Society.

2. Income Tax Status and Income Taxes ECS and its Divisions, Groups, and Sections qualify as a tax-exempt organization described under Section 501(c)(3) of the Internal Revenue Code and all of its income, except income generated through the advertising included in its publications, is exempt from Federal income taxes.

As a single-member limited liability company, the LLC is treated as a “disregarded entity” for income tax purposes and, as such, its financial activity is reported in conjunction with the Federal income tax filings of ECS. The Society has adopted the accounting pronouncement that provides guidance on uncertain tax positions.

The Society has no unrecognized tax benefits at December 31, 2015.

3. Investments Investments in equities and fixed income instruments are reported at fair market value, and investment in real estate is reported at cost.

Investment income and realized and unrealized net gains and losses on investments of permanently restricted net assets are reported as follows: as increases or decreases in temporarily restricted net assets if the terms of the gift impose restrictions on the use of the income and/or net gains; as increases or decreases in unrestricted net assets in all other cases. Cost, market value and unrealized appreciation (depreciation) at December 31, 2015 are summarized as follows: Cost

Money market funds

$

Market Value

8,517

$

8,517

Unrealized Appreciation (Depreciation) $

--

Stocks and mutual funds

8,396,124

8,840,500

444,376

Certificate of deposit

105,678

105,678

--

Corporate and U.S. bonds

1,825,091

1,991,905

166,814

Real estate

5,007,611

5,007,611

--

250,000

295,313

45,313

$15,593,021

$16,249,524

$ 656,503

Real Estate Trust Total

5. ECS Holdings, LLC ECS Holdings LLC was chartered in 1998 to manage the real estate assets of the Society. Current real estate holdings include five buildings at Howe Commons in Pennington, NJ valued at a cost of $5,007,611. The Society occupies one of the buildings and the other four are classified as an investment. The LLC leases office space in these four buildings to various tenants under operating leases arrangements expiring through 2021. Rental income under the aforementioned leases totaled $516,324 (excluding intercompany rentals of $91,740) for the year ended December 31, 2015.

Report of the ECS Audit Committee The ECS Audit Committee provides oversight of The Electrochemical Society’s financial reporting process on behalf of the Board of Directors. Management (ECS Staff Directors and Officers) is responsible for the financial statements and the financial reporting process, including the system of internal control. In fulfilling its oversight responsibilities, the Committee discussed the financial statements in the annual report with management, including a discussion of quality, not just the acceptability, of the accounting principles; the reasonableness of significant judgments; and the clarity of disclosures in the financial statements.

The members of the Audit Committee in 2015 were Paul Kohl (Chair), Krishnan Rajeshwar, E. Jennings Taylor, Daniel Scherson and Stuart Swirson.

The ECS Audit Committee discussed with the independent auditors the overall scope and plans for their respective audits. The Committee meets with the independent auditors with and without management present, to discuss the results of their examinations, their evaluations of the Society’s internal control, compliance with laws and regulations, and the overall quality of the Society’s financial reporting.

Based on the discussions referenced above, the ECS Audit Committee recommended for acceptance to the Board of Directors the audited financial statements for the year ended December 31, 2015 and the Board unanimously approved.

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2015 Y e a r in RE vie w

ECS Student Chapters ECS Student Chapter (Year Founded)

Faculty Advisor

Atlanta Student Chapter at Georgia Tech (2008)

Peter J. Hesketh

Auburn University (2007)

Majid Beidaghi

Belgium (2015)

Stefan De Gendt Philippe Vereecken

Boston (2009) Northeastern University Harvard University MIT British Columbia (2013) University of British Columbia Simon Fraser University University of Victoria

Eugene Smotkin

Dan Bizzotto

Brno University of Technology (2006)

Jiri Vondrak

Calgary (2011)

Viola Birss

California State University (2012) Fullerton Division

John Haan

Central Illinois (2008)

Andrzej Wieckowski

Clemson University (2014)

Stephen Creager

ECS Cleveland Section and Ernest B. Yeager Center for Electrochemical Sciences Joint Student Chapter (2005)

James D. Burgess

Colorado School of Mines (2012)

Andrew Herring

Drexel University (2012) Illinois Institute of Technology (2015) Indiana University (2012)

Yury Gogotsi Ekaterina Pomerantseva Vijay Ramani Adam Hock Lane Baker Dennis Peters

Kerala, India at CUSAT (2008)

M. K. Jayaraj

Lewis University (2015)

Jason J. Keleher

Lahore, Pakistan (2008)

Inam Ul Haque

Montana State University (2013)

Paul Gannon Ryan Anderson

Montreal (2010)

Steen B. Schougaard

Munich (2015)

Hubert Gasteiger

New Mexico State University (2015)

Vimal Chaitanya Hongmei Luo

North Florida (2014)

Pedro Moss

Norwegian University of Science and Technology (2014)

Ann Mari Svensson

Ohio State University (2006)

Anne Co

Ohio University (2011)

Gerardine Botte

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2015 Y e a r in Re vie w

ECS Student Chapter (Year Founded)

Faculty Advisor

Rensselaer Polytechnic Institute (2013)

Daniel Lewis David Duquette

Research Triangle Student Chapter (2013) Duke University NC State UNC – Chapel Hill

Jeffrey Glass (Duke)

South Brazilian (Univ. Fed. do Rio Grande do Sul) (2010)

Luis Frederico P. Dick

SRM University (2013) Tel Aviv University (2009)

Ranjit Thapa Bhalchandra Kakade Eliezer Gileadi Yosi Shacham-Diamand

Tyndall National Institute (2012)

Alan O’Riordan

U.K. Northwest (2015)

Laurence Hardwick

University of Arkansas (2014)

Rick Wise Ingrid Fritsch

University of California – Berkeley (2006)

Bryan McCloskey

University of California – Los Angeles (2015)

Sarah Tolbert

University of California – Riverside (2011)

Alexander Balandin

University of California – San Diego (2014)

Shirley Meng

University of Central Florida (2000)

Kalpathy Sundaram

University of Cincinnati (2007)

Marc Cahay

University of Florida (2005)

Mark Orazem

University of Iowa (2014)

Johna Leddy

University of Kentucky (2014)

Mona Shirpour

University of Maryland (2011)

Eric Wachsman

University of Nevada – Reno (2014)

Dev Chidambaram

University of Pittsburgh (2014)

Prasanth Kumta

University of Saint Andrews (2015)

John T. S. Irvine Mark Cassidy

University of South Carolina (2010)

Xiao-dong Zhou

University of Tartu (2013)

Kaido Tammeveski

University of Texas at Austin (2006)

Ram Manthiram

University of Texas at Dallas (2012)

Moon Kim

University of Utah (2015)

Shelley Minteer Henry White

University of Virginia (2006)

Giovanni Zangari

Valley of the Sun (Central Arizona) (2013)

Candace Chan

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2015 Y e a r in RE vie w

ECS Editorial Boards Electrochemical Science & Technology Journals Robert F. Savinell, Editor Doron Aurbach, Technical Editor Gerald S. Frankel, Technical Editor Thomas F. Fuller, Technical Editor Charles L. Hussey, Technical Editor Shelley D. Minteer, Technical Editor

(as of December 31, 2015)

Elizabeth Podlaha-Murphy, Electrodeposition Division Representative Jerzy Ruzyllo, Electronics and Photonics Division Representative Mani Manivannan, Energy Technology Division Representative Paul Gannon, High Temperature Materials Division Representative John Staser, Industrial Electrochemistry & Electrochemical Engineering Division Representative

Rangachary Mukundan, Technical Editor

Uwe Happek, Luminescence and Display Materials Division Representative

Dennis G. Peters, Technical Editor

Slava Rotkin, Nanocarbons Division Representative

John Weidner, Technical Editor

Jim Burgess, Organic and Biological Electrochemistry Division Representative

Thierry Brousse, Associate Editor Raymond J. Gorte, Associate Editor Takayuki Homma, Associate Editor Boryann Liaw, Associate Editor Scott Lillard, Associate Editor Stephen Maldonado, Associate Editor Paul Natishan, Associate Editor Thomas J. Schmidt, Associate Editor Venkat Srinivasan, Associate Editor

Andrew Hillier, Physical and Analytical Electrochemistry Division Representative Nick Wu, Sensor Division Representative

ECS Transactions Jeffrey W. Fergus, Editor Marca Doeff, Battery Division Representative Dev Chidambaram, Corrosion Division Representative

Nae-Lih (Nick) Wu, Associate Editor

Zhi (David) Chen, Dielectric Science and Technology Division Representative

Solid State Science & Technology Journals

Elizabeth Podlaha-Murphy, Electrodeposition Division Representative

Dennis Hess, Editor Jennifer A. Bardwell, Technical Editor Stefan De Gendt, Technical Editor Francis D’Souza, Technical Editor Kailash C. Mishra, Technical Editor Fan Ren, Technical Editor George Celler, Associate Editor

Interface Vijay Ramani, Co-Editor Petr Vanýsek, Co-Editor Robert Kostecki, Battery Division Representative Sanna Virtanen, Corrosion Division Representative

D. Noel Buckley, Electronics and Photonics Division Representative James M. Fenton, Energy Technology Division Representative Cortney Kreller, High Temperature Materials Division Representative John Harb, Industrial Electrochemistry & Electrochemical Engineering Division Representative Kailash C. Mishra, Luminescence and Display Materials Division Representative R. Bruce Weisman, Nanocarbons Division Representative James Burgess, Organic and Biological Electrochemistry Division Representative Petr Vanýsek, Physical and Analytical Electrochemistry Division Representative Dong-Joo Kim, Sensor Division Representative

Durga Misra, Dielectric Science and Technology Division Representative

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ECS Honor Roll Past Presidents of the Society J. W. Richards............................... 1902-1904 H. S. Carhart................................. 1904-1905 W. D. Bancroft............................... 1905-1906 C. Hering....................................... 1906-1907 C. F. Burgess................................. 1907-1908 E. G. Acheson................................ 1908-1909 L. H. Baekeland............................. 1909-1910 W. H. Walker................................. 1910-1911 W. R. Whitney............................... 1911-1912 W. L. Miller.................................... 1912-1913 E. F. Roeber................................... 1913-1914 F. A. Lidbury.................................. 1914-1915 L. Addicks..................................... 1915-1916 F. A. J. FitzGerald........................... 1916-1917 C. G. Fink...................................... 1917-1918 F. J. Tone....................................... 1918-1919 W. D. Bancroft............................... 1919-1920 W. S. Landis.................................. 1920-1921 A. Smith........................................ 1921-1922 C. G. Schluederberg.................................1922-1923 A. T. Hinckley................................ 1923-1924 H. C. Parmelee.............................. 1924-1925 F. M. Becket................................... 1925-1926 W. Blum........................................ 1926-1927 S. C. Lind...................................... 1927-1928 P. J. Kruesi.................................... 1928-1929 F. C. Frary...................................... 1929-1930 L. Kahlenberg................................ 1930-1931 B. Stoughton................................. 1931-1932 R. A. Witherspoon......................... 1932-1933 J. Johnston................................... 1933-1934 H. S. Lukens.................................. 1934-1935 J. H. Critchett................................ 1935-1936 D. A. MacInnes.............................. 1936-1937 W. G. Harvey................................. 1937-1938 R. L. Baldwin................................. 1938-1939 H. J. Creighton.............................. 1939-1940

F. C. Mathers................................. 1940-1941 R. R. Ridgway............................... 1941-1942 E. M. Baker.................................... 1942-1943 R. M. Burns................................... 1943-1944 S. D. Kirkpatrick............................ 1944-1945 W. R. Veazey................................. 1945-1946 W. C. Moore.................................. 1946-1947 G. W. Heise................................... 1947-1948 J. A. Lee........................................ 1948-1949 A. L. Ferguson............................... 1949-1950 C. L. Faust..................................... 1950-1951 R. M. Hunter................................. 1951-1952 J. C. Warner.................................. 1952-1953 R. J. McKay................................... 1953-1954 M. J. Udy...................................... 1954-1955 H. H. Uhlig.................................... 1955-1956 H. Thurnauer................................. 1956-1957 N. Hackerman............................... 1957-1958 S. Swann....................................... 1958-1959 W. C. Gardiner............................... 1959-1960 R. A. Schaefer............................... 1960-1961 H. B. Linford.................................. 1961-1962 F. L. LaQue.................................... 1962-1963 W. J. Hamer.................................. 1963-1964 L. I. Gilbertson.............................. 1964-1965 E. B. Yeager................................... 1965-1966 H. J. Read..................................... 1966-1967 H. C. Gatos.................................... 1967-1968 I. E. Campbell................................ 1968-1969 N. C. Cahoon................................. 1969-1970 C. W. Tobias.................................. 1970-1971 C. V. King...................................... 1971-1972 T. D. McKinley............................... 1972-1973 N. B. Hannay................................. 1973-1974 D. A. Vermilyea............................. 1974-1975 T. R. Beck...................................... 1975-1976 M. J. Pryor.................................... 1976-1977

D. N. Bennion................................ 1977-1978 D. R. Turner.................................. 1978-1979 J. B. Berkowitz.............................. 1979-1980 E. M. Pell....................................... 1980-1981 R. J. Brodd.................................... 1981-1982 F. J. Strieter................................... 1982-1983 J. B. Wagner, Jr............................. 1983-1984 P. C. Milner.................................... 1984-1985 R. C. Alkire.................................... 1985-1986 R. E. Enstrom................................ 1986-1987 F. G. Will........................................ 1987-1988 B. E. Deal...................................... 1988-1989 E. J. Cairns.................................... 1989-1990 J. M. Woodall................................ 1990-1991 L. R. Faulkner................................ 1991-1992 W. L. Worrell................................. 1992-1993 R. P. Frankenthal........................... 1993-1994 J. A. Amick.................................... 1994-1995 K. R. Bullock................................. 1995-1996 D. W. Hess.................................... 1996-1997 B. Miller........................................ 1997-1998 G. M. Blom.................................... 1998-1999 D. E. Hall....................................... 1999-2000 C. M. Osburn................................. 2000-2001 J. Talbot........................................ 2001-2002 K. Spear........................................ 2002-2003 B. Scrosati.................................... 2003-2004 R. Susko....................................... 2004-2005 W. Smyrl....................................... 2005-2006 Mark Allendorf.............................. 2006-2007 Barry MacDougall......................... 2007-2008 D. Noel Buckley............................. 2008-2009 Paul Natishan................................ 2009-2010 William D. Brown.......................... 2010-2011 Esther S. Takeuchi......................... 2011-2012 Fernando Garzon........................... 2012-2013 Tetsuya Osaka............................... 2013-2014 Paul Kohl....................................... 2014-2015

H. B. Linford.................................. 1949-1959 I. E. Campbell................................ 1959-1965 R. F. Bechtold................................ 1965-1968 D. R. Turner.................................. 1968-1974 P. C. Milner.................................... 1974-1980 F. A. Trumbore............................... 1980-1984

J. A. Amick.................................... 1984-1988 E. W. Brooman.............................. 1988-1992 J. McBreen.................................... 1992-1996 R. Susko....................................... 1996-2000 P. Natishan.................................... 2000-2004 P. Vanýsek..................................... 2004-2008 J. Leddy........................................ 2008-2012

E. G. Enck...................................... 1961-1964 R. H. Schaefer............................... 1964-1967 R. H. Cherry.................................. 1967-1973 F. J. Strieter................................... 1973-1976 J. L. Griffin.................................... 1976-1982 J. Kruger....................................... 1982-1986 R. P. Frankenthal........................... 1986-1990

R. E. White.................................... 1990-1994 W. M. Bullis................................... 1994-1997 Y. H. Wong.................................... 1997-1998 W. D. Brown.................................. 1998-2002 P. Fedkiw....................................... 2002-2006 J. Susko........................................ 2006-2010 Christina Bock............................... 2010-2014

Past Secretaries of the Society C. Hering.................................................1902 C. J. Reed...................................... 1902-1904 S. S. Sadtler.................................. 1904-1907 J. W. Richards............................... 1907-1921 C. G. Fink...................................... 1921-1947 R. M. Burns................................... 1947-1949

Past Treasurers of the Society P. G. Salom................................... 1902-1920 F. A. Lidbury.................................. 1920-1924 A. Smith........................................ 1924-1931 R. M. Burns................................... 1931-1943 W. W. Winship............................... 1943-1949 E. G. Widell................................... 1949-1955 L. I. Gilbertson.............................. 1955-1961

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Edward Goodrich Acheson Award E. G. Acheson...........................................1929 E. F. Northrup...........................................1931 C. G. Fink.................................................1933 F. J. Tone..................................................1935 F. M. Becket..............................................1937 F. C. Frary.................................................1939 C. F. Burgess............................................1942 W. Blum...................................................1944 H. J. Creighton.........................................1946 D. A. MacInnes.........................................1948 G. W. Vinal...............................................1950 J. W. Marden............................................1952 G. W. Heise..............................................1954 R. M. Burns..............................................1956 W. J. Kroll................................................1958 H. B. Linford.............................................1960 C. L. Faust................................................1962 E. A. Gulbransen......................................1964 W. C. Vosburgh........................................1966 F. L. LaQue...............................................1968 S. Ruben..................................................1970 C. W. Tobias.............................................1972 C. V. King.................................................1974 N. B. Hannay............................................1976 D. A. Vermilyea........................................1978 E. B. Yeager..............................................1980 H. C. Gatos...............................................1982 N. Hackerman..........................................1984 E. M. Pell..................................................1986 H. H. Uhlig...............................................1988 T. R. Beck.................................................1990 D. R. Turner.............................................1992 J. B. Wagner, Jr........................................1994 R. C. Alkire...............................................1996 J. M. Woodall...........................................1998 L. R. Faulkner...........................................2000 B. Deal.....................................................2002 W. L. Worrell............................................2004 V. de Nora................................................2006 Robert P. Frankenthal...............................2008 John Newman..........................................2010 Dennis Hess.............................................2012 Ralph J. Brodd.........................................2014

Olin Palladium Medal Award (formerly the Palladium Medal Award, 1951-1977)

C. W. Wagner...........................................1951 N. H. Furman............................................1953 U. R. Evans..............................................1955 K. F. Bonhoeffer........................................1957

A. N. Frumkin...........................................1959 H. H. Uhlig...............................................1961 N. Hackerman..........................................1965 P. Delahay................................................1967 T. P. Hoar..................................................1969 L. Brewer.................................................1971 V. G. Levich..............................................1973 M. J. N. Pourbaix.....................................1975 H. Gerischer.............................................1977 R. Parsons...............................................1979 I. M. Kolthoff............................................1981 M. Cohen.................................................1983 M. Fleischmann........................................1985 A. J. Bard.................................................1987 B. E. Conway............................................1989 J. Newman...............................................1991 J.-M. Savéant...........................................1993 J. Kruger..................................................1995 R. W. Murray............................................1997 J. B. Goodenough....................................1999 N. Sato.....................................................2001 E. Gileadi..................................................2003 R. Rapp....................................................2005 Sergio Trasatti..........................................2007 Dieter M. Kolb..........................................2009 Koji Hashimoto........................................2011 Ralph White.............................................2013 Digby Macdonald.....................................2015

Gordon E. Moore Medal for Outstanding Achievement in Solid-State Science and Technology (formerly the Solid State Science & Technology Award, 1973-2005)

W. G. Pfann..............................................1973 H. C. Gatos...............................................1975 R. N. Hall..................................................1977 M. B. Panish.............................................1979 G. L. Pearson...........................................1981 N. Holonyak, Jr.........................................1983 J. M. Woodall...........................................1985 A. Y. Cho..................................................1987 J. F. Gibbons............................................1989 J. D. Plummer..........................................1991 B. E. Deal.................................................1993 W. L. Worrell............................................1995 K. E. Spear...............................................1997 I. Akasaki.................................................1999 A. Reisman...............................................2001 R. B. Fair..................................................2003 D. Hess....................................................2005 Tak H. Ning..............................................2007 C. Grant Willson.......................................2009 Stephen Pearton......................................2011 Fan Ren....................................................2013 Yue Kuo...................................................2015

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Vittorio de Nora Award in Electrochemical Engineering and Technology (formerly the Electrochemical Science and Technology Award, 1974-1977)

A. Brenner................................................1974 R. B. MacMullin.......................................1976 F. T. Bacon................................................1978 H. B. Beer.................................................1980 J. C. Schumacher.....................................1982 D. E. Danly...............................................1984 K. Kordesch.............................................1986 A. Heller...................................................1988 C. W. Tobias.............................................1990 E. B. Yeager..............................................1992 L. T. Romankiw........................................1994 R. Baboian...............................................1996 W. G. Grot................................................1998 D. R. Turner.............................................2000 R. C. Alkire...............................................2004 F. Mansfeld...............................................2006 John S. Newman......................................2008 Derek Pletcher..........................................2010 Bruno Scrosati.........................................2012 Chad Mirkin..............................................2014

Carl Wagner Memorial Award A. J. Bard.................................................1981 G. C. Wood...............................................1983 R. C. Alkire...............................................1985 R. W. Murray............................................1987 W. L. Worrell............................................1989 D. D. Macdonald .....................................1991 J. Jorné....................................................1993 B. R. MacDougall.....................................1995 M. J. Weaver............................................1997 C. R. Martin..............................................1999 P. A. Kohl.................................................2001 R. M. Crooks............................................2003 J. Hupp....................................................2005 Philip N. Bartlett.......................................2007 Henry S. White.........................................2009 Peter Bruce..............................................2011 Marc T. M. Koper......................................2013 Martin Winter...........................................2015

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Henry B. Linford Award for Distinguished Teaching C. W. Tobias.............................................1982 B. E. Conway............................................1984 A. J. Bard.................................................1986 L. Brewer.................................................1988 J. Newman...............................................1990 K. Nobe....................................................1992 J. O’M. Bockris.........................................1994 T. C. Franklin............................................1996 R. A. Rapp................................................1998 G. Stoner..................................................2000 D. Peters..................................................2002 R. M. Latanision.......................................2004 D. Pletcher...............................................2006 Eliezer Gileadi...........................................2008 Daniel T. Schwartz....................................2010 Mark E. Orazem........................................2012 Dennis Hess.............................................2014

Charles W. Tobias Young Investor Award Stuart B. Adler..........................................2004 Hock Min Ng............................................2006 Yang Shao-Horn.......................................2008 Thomas J. Schmidt..................................2010 Bryan S. Pivovar......................................2012 Bilge Yildiz...............................................2012 Adam Weber............................................2014

Allen J. Bard Award Henry White.............................................2015

Honorary Members Charles F. Chandler..................................1919 Edgar F. Smith..........................................1919 Carl Hering...............................................1922 Edward G. Acheson..................................1923 Wilder D. Bancroft....................................1925 Edward Weston........................................1926 Thomas A. Edison....................................1928 W. Lash Miller..........................................1929 Edward Dean Adams................................1930 Charles F. Burgess....................................1932 Frederick M. Becket..................................1934 L. H. Baekeland........................................1936 Robert A. Witherspoon............................1940 Archer E. Wheeler....................................1941 W.R. Whitney...........................................1944 Paul J. Kruesi...........................................1944

Colin G. Fink.............................................1946 Oliver W. Brown.......................................1946 John W. Marden.......................................1947 William Blum............................................1953 Robert M. Burns......................................1959 George W. Heise......................................1959 Frank C. Mathers......................................1959 Stanislaus Skowronski.............................1962 Oliver W. Storey.......................................1962 A. Kenneth Graham..................................1963 Howard A. Acheson..................................1971 Charles L. Faust.......................................1971 Cecil V. King.............................................1973 Herbert H. Uhlig.......................................1973 Norman Hackerman.................................1973 Henry B. Linford.......................................1974 Sherlock Swann.......................................1974 Ernest G. Enck..........................................1975 W. C. Gardiner..........................................1975 Ivor E. Campbell.......................................1976 Ernest B. Yeager.......................................1977 David A. Vermilyea...................................1977 Charles W. Tobias.....................................1977 Harry C. Gatos.........................................1978 Ralph M. Hunter.......................................1979 Dennis R. Turner......................................1980 Henry F. Ivey............................................1980 Walter J. Hamer.......................................1980 Michael J. Pryor.......................................1981 Francis L. LaQue......................................1981 N. Bruce Hannay......................................1982 Theodore R. Beck.....................................1982 Vittorio de Nora........................................1982 John L. Griffin..........................................1983 Erik M. Pell...............................................1983 Samuel Ruben..........................................1983 Paul C. Milner..........................................1986 Harold J. Read.........................................1986 Forrest A. Trumbore.................................1986 Douglas N. Bennion.................................1987 Ralph J. Brodd.........................................1987 Jerome Kruger.........................................1987 Glenn W. Cullen........................................1990 James C. Acheson....................................1990 Richard C. Alkire......................................1991 Bertram Schwartz....................................1991 J. Bruce Wagner, Jr..................................1991 V. H. Branneky..........................................1991 R. S. Karpiuk............................................1996 F. J. Strieter..............................................1996 W. L. Worrell............................................1996 Barry Miller..............................................1999 Jefferson Cole..........................................2001 L. Faulkner...............................................2003 R. Frankenthal..........................................2003 L. Romankiw............................................2003 Gordon E. Moore......................................2007 John S. Newman......................................2007 Jerry M. Woodall......................................2007 Allen J. Bard.............................................2013 John B. Goodenough...............................2013 Adam Heller.............................................2015

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Fellows of The Electrochemical Society Allen J. Bard.............................................1990 Robert B. Comizzoli..................................1990 Glenn W. Cullen........................................1990 Theodore I. Kamins..................................1990 Paul C. Milner..........................................1990 Edward H. Nicollian..................................1990 Robert A. Osteryoung..............................1990 Arnold Reisman.......................................1990 Lubomyr T. Romankiw.............................1990 Geraldine C. Schwartz..............................1990 Ben G. Streetman.....................................1990 J. Bruce Wagner, Jr..................................1990 Theodore R. Beck.....................................1991 Elton J. Cairns..........................................1991 Bruce E. Deal............................................1991 Werner Kern.............................................1991 William A. Pliskin.....................................1991 Charles W. Tobias.....................................1991 Rolf Weil..................................................1991 Richard C. Alkire......................................1992 Vittorio de Nora........................................1992 Jerome Kruger.........................................1992 Barry Miller..............................................1992 Dennis R. Turner......................................1992 Jerry M. Woodall......................................1992 Richard P. Buck........................................1993 Larry. R. Faulkner.....................................1993 Dennis W. Hess........................................1993 Vik J. Kapoor............................................1993 Rolf H. Muller...........................................1993 Carlton M. Osburn....................................1993 Robert A. Rapp........................................1993 George L. Schnable..................................1993 Y. H. Wong...............................................1993 Petr Zuman..............................................1993 George K. Celler.......................................1994 Sung-Nee George Chu.............................1994 John P. Dismukes....................................1994 Richard B. Fair.........................................1994 Adam Heller.............................................1994 Richard A. Oriani......................................1994 Boone B. Owens.......................................1994 Wayne L. Worrell.....................................1994 Fred Anson...............................................1995 Laurence D. Burke....................................1995 Brian E. Conway.......................................1995 Robert P. Frankenthal...............................1995 Karl M. Kadish..........................................1995 Digby D. Macdonald.................................1995 Gleb Mamantov........................................1995 Florian Mansfeld......................................1995 Royce W. Murray.....................................1995 John Newman..........................................1995 Yutaka Okinaka.........................................1995 Howard W. Pickering................................1995 George Rozgonyi......................................1995 Mordechay Schlesinger............................1995 Karl E. Spear............................................1995 John M. Blocher, Jr..................................1996 Hans K. Böhni..........................................1996 85

2015 Y e a r in RE vie w Fellows (continued) Der-Tau Chin............................................1996 Hugh Isaacs.............................................1996 Wolfgang J. Lorenz..................................1996 S. J. Pearton............................................1996 Subhash C. Singhal..................................1996 Venkataraman Swaminathan....................1996 James A. Amick.......................................1997 Denis Noel Buckley..................................1997 Eliezer Gileadi...........................................1997 Michel J. Froment....................................1997 Koji Hashimoto........................................1997 Chung-Chiun Liu......................................1997 Edward McCafferty..................................1997 Theodore D. Moustakas...........................1997 Shyam P. Muraka.....................................1997 Stella W. Pang..........................................1997 Joachim Walter Schultze..........................1997 James D. Sinclair.....................................1997 Norman L. Weinberg................................1997 Lawrence Young......................................1997 Huk Y. Cheh..............................................1998 Donald E. Danly........................................1998 Dennis H. Evans.......................................1998 Fumio Hine...............................................1998 Dennis C. Johnson...................................1998 Zoltan Nagy..............................................1998 Katsumi Niki.............................................1998 Jun-ichi Nishizawa...................................1998 Fan Ren....................................................1998 Antonio J. Ricco.......................................1998 David A. Shores.......................................1998 William H. Smyrl......................................1998 George Thompson...................................1998 Eric Brooman...........................................1999 Stanley Bruckenstein................................1999 Kathryn Bullock........................................1999 Shimshon Gottesfeld................................1999 Yue Kuo...................................................1999 Dieter Landolt..........................................1999 Jerzy Ruzyllo............................................1999 Norio Sato................................................1999 Ralph White.............................................1999 William Yen..............................................1999 Cammy Abernathy....................................2000 Kuzhikalail M. Abraham............................2000 John C. Angus..........................................2000 W. Ronald Fawcett...................................2000 David S. Ginley.........................................2000 Yasuhiko Ito.............................................2000 Howard Huff.............................................2000 Robert F. Savinell.....................................2000 Roger Staehle..........................................2000 Charles W. Struck....................................2000 Sergio Trasatti..........................................2000 Dieter M. Kolb..........................................2001 David J. Lockwood...................................2001 James McBreen.......................................2001 Patrick J. Moran.......................................2001 Shohei Nakahara......................................2001 William E. O’Grady...................................2001

Supramanian Srinivasan..........................2001 Mark Allendorf.........................................2002 William Brown..........................................2002 Cor Claeys................................................2002 Martin Kendig..........................................2002 Kim Kinoshita...........................................2002 Paul Kohl..................................................2002 Zempachi Ogumi......................................2002 Tetsuya Osaka..........................................2002 Krishnan Rajeshwar.................................2002 Israel Rubinstein......................................2002 Sigeru Torii..............................................2002 Toshio Shibata.........................................2002 Sorin Cristoloveanu..................................2002 David Duquette........................................2003 Peter Fedkiw............................................2003 Charles Hussey........................................2003 Richard McCreery....................................2003 Frank McLarnon.......................................2003 Robin Susko............................................2003 Darrel Untereker.......................................2003 Osamu Yamamoto....................................2003 G. T. Burstein...........................................2004 C. Clayton.................................................2004 G. Davis...................................................2004 M. J. Deen................................................2004 S. Fonash.................................................2004 M. Meyyappan.........................................2004 J. F. Rusling.............................................2004 M. Seo.....................................................2004 M. Shur....................................................2004 J. Simonet................................................2004 M. Stratmann...........................................2004 J. Talbot...................................................2004 M. S. Whittingham...................................2004 R. Adzic....................................................2005 J. Davidson..............................................2005 T. Hattori..................................................2005 J. P. Leburton...........................................2005 P. Marcus.................................................2005 C. Martin..................................................2005 P. Natishan...............................................2005 D. Pletcher...............................................2005 B. Scrosati...............................................2005 J. Scully...................................................2005 R. Singh...................................................2005 H. H. Strehblow........................................2005 M. Williams..............................................2005 A. Baca.....................................................2006 S. Bandyopadhyay...................................2006 T. Fahidy...................................................2006 G. Frankel.................................................2006 C. Jagadish..............................................2006 N. Koshida...............................................2006 J. Lessard................................................2006 H. Massoud..............................................2006 H. Yokokawa............................................2006 B. MacDougall..........................................2006 M. Orazem...............................................2006 D. Misra...................................................2006 A. Virkar...................................................2006 A. Wieckowski..........................................2006

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Simon S. Ang...........................................2007 Viola Birss................................................2007 Marc Cahay..............................................2007 James M. Fenton......................................2007 Dennis G. Peters......................................2007 Daniel A. Scherson...................................2007 Eric D. Wachsman....................................2007 Doron Aurbach.........................................2008 Albert J. Fry.............................................2008 Fernando Garzon......................................2008 Yury Gogotsi............................................2008 Curtis F. Holmes.......................................2008 Prashant V. Kamat....................................2008 Patrik Schmuki.........................................2008 Gery R. Stafford.......................................2008 Joseph R. Stetter.....................................2008 John Stickney..........................................2008 Thomas Thundat......................................2008 Vladimir Bagotsky....................................2009 Ugo Bertocci............................................2009 Manfred Engelhardt..................................2009 Tom Fuller................................................2009 Peter Hesketh...........................................2009 Uziel Landau............................................2009 Dolf Landheer..........................................2009 Thomas P. Moffat.....................................2009 Ikuzo Nishiguchi......................................2009 Kohei Uosaki............................................2009 Rudolph G. Buchheit................................2010 Francis D’Souza.......................................2010 Toshio Fuchigami.....................................2010 Michel Houssa.........................................2010 Robert G. Kelly.........................................2010 Roger C. Newman....................................2010 Peter N. Pintauro......................................2010 Peter C. Searson......................................2010 David Shoesmith......................................2010 Bernard Tribollet......................................2010 John W. Weidner......................................2010 David J. Young.........................................2010 Hugh C. DeLong.......................................2011 Hubert Gasteiger......................................2011 Arumugam Manthiram.............................2011 Ashok Kumar Shukla................................2011 Paul C. Trulove.........................................2011 Karim Zaghib............................................2011 Giovanni Zangari......................................2011 Thomas A. Zawodzinski...........................2011 Jeffrey R. Dahn........................................2012 Stefan DeGendt........................................2012 Hariklia Deligianni....................................2012 Andrew Gewirth.......................................2012 Meilin Liu.................................................2012 Junichi Murota.........................................2012 Sri Narayan..............................................2012 Trung Van Nguyen....................................2012 Winston Revie..........................................2012 Daniel Schwartz.......................................2012 Esther Takeuchi........................................2012 Mark Verbrugge.......................................2012 Petr Vanýsek............................................2012 Bruce Weisman........................................2012

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2015 Y e a r in Re vie w Fellows (continued) Hector Abruña..........................................2013 Nancy Dudney..........................................2013 Gary Hunter.............................................2013 Jiri Janata................................................2013 Johna Leddy............................................2013 Shelley Minteer........................................2013 Sanjeev Mukerjee.....................................2013 Elizabeth Opila..........................................2013 Jan Robert Selman...................................2013 Kalpathy Sundaram..................................2013 Enrico Traversa........................................2013 Martin Winter...........................................2013 George E. Blomgren.................................2014 Gerardine Botte........................................2014 Ralph J. Brodd.........................................2014 Yasuhiro Fukunaka...................................2014 Jay W. Grate.............................................2014 Dirk Guldi.................................................2014 Bruce Parkinson.......................................2014 Fred Roozeboom......................................2014 Alvin Salkind............................................2014 Sudipta Seal.............................................2014 Michael Thackeray...................................2014 Tooru Tsuru..............................................2014 Harry Tuller..............................................2014 Jose Zagal................................................2014 Piotr Zelenay............................................2014 Simon Deleonibus....................................2015 Raymond Gorte........................................2015 Ellen Ivers-Tiffeé......................................2015 Deborah Jones.........................................2015 Robert Kostecki........................................2015 Mogens Mogensen..................................2015 Kailash Mishra.........................................2015 Emanuel Peled.........................................2015 E. Jennings Taylor....................................2015 John Turner..............................................2015 Steven Visco............................................2015

Edward G. Weston Summer Fellowship

(formerly the Edward G. Weston Fellowship, 1930-1945)

E. B. Sanigar............................................1930 K. Solliner................................................1931 M. E. Fogle...............................................1932 R. D. Blue.................................................1933 P. A. Jacquet............................................1934 M. A. Coler...............................................1935 H. B. Linford.............................................1936 G. L. Putnam............................................1937 V. de Nora................................................1938 W. P. Ruemmier.......................................1940 R. E. Black................................................1941 W. E. Roake..............................................1942 R. D. Misch..............................................1947 M. T. Simnad............................................1948 R. L. Brubaker..........................................1961 D. Yohe....................................................1962 H. O. Daley, Jr..........................................1963 M. D. Hawley............................................1964

T. G. McCord............................................1965 J. D. McLean............................................1966 K. B. Prater...............................................1967 K. Doblhofer.............................................1968 L. R. Faulkner...........................................1969 W. J. Horkans...........................................1970 W. J. Horkans...........................................1971 W. J. Bover...............................................1972 B. J. Alexander.........................................1973 S. S. Fratoni, Jr. ......................................1974 M. Suchanski...........................................1975 R. J. Nowak..............................................1976 P. A. Kohl.................................................1977 C. D. Jaeger.............................................1978 L. Bottomley.............................................1979 G. L. McIntire...........................................1980 J. Pemberton...........................................1981 M. E. Kordesch.........................................1982 R. G. Tompson.........................................1983 P. M. Kovach............................................1984 J. N. Harb.................................................1985 S. E. Creager............................................1986 X. Zhang...................................................1987 C. Amass..................................................1988 R. J. Phillips.............................................1989 J. E. Franke..............................................1990 S. R. Snyder.............................................1991 P. Pantano................................................1992 G. J. Edens...............................................1993 B. Idriss...................................................1994 D. Bizzotto................................................1995 L. A. Lyon.................................................1996 C. Claypool...............................................1997 B. Bath.....................................................1998 A. C. Templeton........................................1999 P. W. Wuelfing..........................................2000 K. Balss....................................................2001 T. Hu........................................................2002 J. Mauzeroll.............................................2003 J. Seegmiller............................................2004 E. Blair.....................................................2005 F. Laforge.................................................2006 Aleix G. Güell............................................2007 Matthew J. Banholzer...............................2008 Shulei Chou..............................................2009 Binh-Minh Nguyen...................................2010 Abrin Schmucker.....................................2011 Sujat Sen..................................................2012 Philippe Dauphin Ducharme.....................2013 Tuncay Ozel..............................................2014 Gen Chen.................................................2015

Colin Garfield Fink Summer Fellowship P. Brown...................................................1962 W. G. Lemmermann.................................1963 W. G. Stevens...........................................1964 J. P. Carney..............................................1965 S. Piekarski..............................................1966 B. S. Pons................................................1967 R. E. Bonewitz..........................................1968 L. Papouchado.........................................1969

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R. G. Reed................................................1970 R. Fike......................................................1971 D. L. McAllister........................................1972 R. R. Chance............................................1973 P. I. Lee....................................................1974 J. B. Flanagan...........................................1975 J. S. Hammond........................................1976 P. D. Tyma................................................1977 S. M. Wilhelm..........................................1978 J. D. Porter...............................................1979 R. S. Glass...............................................1980 E. E. Bancroft...........................................1981 T. D. Cabeika............................................1982 B. L. Wheeler...........................................1983 E. T. T. Jones............................................1984 D. A. Van Galen........................................1985 J. S. Hanson.............................................1986 P. Gao.......................................................1987 D. T. Schwartz..........................................1988 A. E. Russell.............................................1989 J. Xue.......................................................1990 C. K. Rhee................................................1991 M. J. Shane..............................................1992 C. M. Pharr...............................................1993 J. M. Lauerhaus.......................................1994 S. M. Hendrickson...................................1995 J. C. Hutchinson.......................................1996 P. V. A. Pamidi..........................................1997 G. S. Hwang.............................................1998 W. Baker...................................................1999 A. Crown..................................................2000 R. Maus...................................................2001 S. Peper...................................................2002 M. Alpuche-Aviles....................................2003 A. Mugweru.............................................2004 G. Lica......................................................2005 A. Martinson............................................2006 Prabeer Barpanda....................................2007 Sau Yen Chew..........................................2008 Hyea Kim..................................................2009 Brian Adams............................................2010 Tae-Ho Shin.............................................2011 Devika Sil.................................................2012 Gabriel G. Rodríguez-Calero.....................2013 Christena K. Nash....................................2014 Hadi Khani................................................2015

Joseph W. Richards Summer Fellowship V. E. Hauser, Jr.........................................1960 M. J. Schaer.............................................1961 R. E. Visco...............................................1961 A. K. Postma............................................1962 C. C. Liu...................................................1963 M. J. Vasile..............................................1964 M. J. Vasile..............................................1965 C. C. Liu...................................................1966 B. N. Baron...............................................1967 L. P. Zajicek, Jr.........................................1968 K. R. Bullock............................................1969 S. H. Cadle...............................................1970 J. W. Webb...............................................1971 87

2015 Y e a r in RE vie w Joseph W. Richards Summer Fellowship (continued)

C. P. Keszthelyi.........................................1972 M. Shabrang............................................1973 D. H. Karweik...........................................1974 T. P. DeAngelis.........................................1975 D. L. Feke.................................................1976 H. Faulkner...............................................1977 D. M. Novak.............................................1978 B. R. Karas...............................................1979 R. M. Cohen.............................................1980 R. N. Dominey..........................................1981 R. M. Ianniello..........................................1982 D. F. Tessier..............................................1983 N. T. Sleszynski........................................1984 C. M. Lieber.............................................1985 J. L. Valdes..............................................1986 R. Q. Bligh................................................1987 D. W. Conrad............................................1988 S. A. Schofield.........................................1989 J. A. Roberts............................................1990 M. S. Freund............................................1991 L. Gao......................................................1992 H. Gasteiger.............................................1993 J. Schoer..................................................1994 S. Morin...................................................1995 N. Madigan...............................................1996 S. Petrovic...............................................1997 J. J. Sumner.............................................1998 A. Wijayawardhana...................................1999 B. Liu.......................................................2000 C. Noble...................................................2001 C. B. France..............................................2002 P. Ramadass............................................2003 J. Carroll..................................................2004 K. Salaita..................................................2005 J. Breger..................................................2006 Sadagopan Krishnan................................2007 Meng Jiang..............................................2008 Haizhou Liu..............................................2009 Mohammad Rez Khajavi...........................2010 Jeyavel Velmurugan.................................2011 Balazs Berkes...........................................2012 Yongjin Lee..............................................2013 Andrey Gunawan......................................2014 Mohammad Mahdi Hasani-Sadrabadi......2015

F. M. Becket Summer Fellowship (formerly the F. M. Becket Memorial Award 1962-1999)

R. B. Johnson..........................................1962 J. K. Johnstone........................................1964 K. Lehman................................................1966 H. K. Bowen.............................................1967 T. E. Parker...............................................1971 G. M. Crosbie...........................................1973 N. A. Godshall..........................................1975 J. D. Hodge..............................................1977 W. Cheng.................................................1979 P. Davies..................................................1981 P. A. Barron..............................................1983 G. J. Miller...............................................1985 M. Rosenbluth.........................................1987

J. D. Cotton..............................................1989 J. Philliber................................................1991 P. Agarwal................................................1993 H. C. Slade...............................................1995 K. S. Weil.................................................1997 G. S. Hwang.............................................1999 J. Parrish.................................................2001 S. Wasileski.............................................2002 E. Clark.....................................................2003 F. Deng.....................................................2004 S. Harrison...............................................2005 Y. Yang.....................................................2006 Michael Orthner.......................................2007 Marcos Jose Leitos Santos......................2008 Steve Rhieu..............................................2009 James Whitaker.......................................2011 Celeste Morris..........................................2012 Carlo Santoro...........................................2013 Brandy Kinkead........................................2014 Raphaële Clément....................................2015

Herbert H.Uhlig Summer Fellowship Natalia Shustova......................................2008 Venkatasubramanian Viswanathan...........2009 Swetha Puchakayala................................2011 Julia van Drunen......................................2012 Junsi Gu...................................................2013 Hadi Tavassol...........................................2014 Alexander Pak..........................................2015

Energy Research Summer Fellowship

(supported by the U.S. Department of Energy)

M. R. Deakin............................................1985 P. B. Johnson...........................................1985 D. A. La Hurd...........................................1985 S. E. Morris..............................................1985 D. P. Wilkinson.........................................1985 D. G. Frank...............................................1986 K.-C. Ho...................................................1986 R. G. Kelly................................................1986 I.-H. Yeo...................................................1986 J. Kwak....................................................1986 L. C. Dash................................................1987 S. A. Naftel...............................................1987 T. R. Nolen...............................................1987 D. Schwartz..............................................1987 T. H. Wong...............................................1987 S. D. Fritts................................................1988 D. A. Koos................................................1988 D. A. Hazlebeck........................................1988 M. O. Schloh............................................1988 S. S. Perine..............................................1988 J. E. Baur.................................................1989 C.-P. Chen................................................1989 D. W. Eng.................................................1989 R. L. McCarley.........................................1989 C. J. Murphy............................................1989 C. K. Nguyen............................................1990 I.-H. Oh....................................................1990 T. G. Strein...............................................1990

88

J. W. Weidner...........................................1990 S. E. Gilbert..............................................1990 C. S. Johnson...........................................1991 H. Huang..................................................1991 D. R. Lawson...........................................1991 B. D. Pendley...........................................1991 C. C. Streinz.............................................1991 P. A. Connick............................................1992 A. C. Hillier...............................................1992 D. L. Taylor...............................................1992 K. K. Lian.................................................1992 T. T. Nadasdi.............................................1992 D. G. Jensen.............................................1993 J. C. Bart..................................................1993 G. Seshadri..............................................1993 J. A. Poirier..............................................1993 K. W. Vogt................................................1993 Z. Shi.......................................................1994 C.-C. Hsueh..............................................1994 V. A. Adamian...........................................1994 K. M. Maness...........................................1994 K. M. Richard...........................................1994 Y.-E. Sung................................................1995 J. C. Conboy.............................................1995 L. A. Zook.................................................1995 W. R. Everett............................................1995 H. Zhang..................................................1995 S. Grabtchak............................................1996 J.-B. Green...............................................1996 S. Motupally.............................................1996 C. Nasr.....................................................1996 S. Nayak...................................................1996 K. Hu........................................................1997 M. E. Williams..........................................1997 A. Zolfaghari.............................................1997 C. R. Horne..............................................1997 G. K. Jennings..........................................1997 M. Zhao....................................................1998 S. Sriramulu.............................................1998 J. Ritchie..................................................1998 M. A. Elhamid...........................................1998 S. Zou......................................................1998 K. Cooper.................................................2000 K. Grant....................................................2000 D. Hansen................................................2000 J. F. Hicks.................................................2000 Z. Liu........................................................2000

Oronzio de Nora Industrial Electrochemistry Fellowship N. Mano...................................................2004 N. Mano...................................................2005 N. Mano...................................................2006 Vijayasekaran Boovaragavan....................2007 Vijayasekaran Boovaragavan....................2008 Vijayasekaran Boovaragavan....................2009 Wenjing (Angela) Zhang...........................2010

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

2015 Y e a r in Re vie w Norman Hackerman Young Author Award (formerly the Young Authors Prize, 1929-1988)

W. C. Gardiner..........................................1929 D. K. Alpern..............................................1930 F. L. Jones................................................1931 F. W. Godsey, Jr........................................1932 B. L. Bailey...............................................1933 J. R. Heard, Jr..........................................1934 U. B. Thomas, Jr......................................1935 W. A. Johnson..........................................1936 R. S. Soanes............................................1937 N. B. Nichols............................................1938 G. A. Moore..............................................1939 J. S. Mackay.............................................1940 E. Adler....................................................1941 S. Speil.....................................................1942 W. G. Berl.................................................1943 J. P. Coyle................................................1944 A. E. Hardy...............................................1945 N. A. Nielsen............................................1946 H. Leidheiser, Jr.......................................1947 M. A. Streicher.........................................1948 J. C. Griess, Jr..........................................1949 G. W. Murphy...........................................1950 J. T. Byrne................................................1951 W. E. Kuhn...............................................1952 J. Halpern.................................................1953 M. J. Pryor...............................................1954 M. Stern...................................................1955 R. S. Cooper.............................................1956 P. Ruetschi...............................................1957 M. Stern...................................................1958 F. A. Posey ..............................................1959 A. C. Makrides..........................................1960 J. D. Newson............................................1961 M. J. Dignam...........................................1962 J. A. Cunningham.....................................1963 R. E. Westerman......................................1964 R. E. Visco...............................................1965 J. Newman...............................................1966 H. W. Pickering........................................1967 G. G. Charette...........................................1968 G. Dryhurst..............................................1969 J. Newman...............................................1969 W. R. Parrish............................................1969 A. J. Appleby............................................1970 D. C. Johnson..........................................1970 D.-T. Chin.................................................1971 M. S. Whittingham...................................1971 M. A. Hopper............................................1972 F. Kuhn-Kuhnenfeld..................................1972 M. J. Bowden...........................................1973 L. Thompson............................................1973 D. Simonsson..........................................1973 S. H. Cadle...............................................1974 A. D. Dalvi................................................1974 L. R. Faulkner...........................................1975 S. Solmi...................................................1975 P. Negrini.................................................1975 B. MacDougall..........................................1976 S. K. Ubhayakar.......................................1976

C. W. Manke.............................................1977 W. J. Horkans...........................................1977 A. G. Gonzalez..........................................1978 C. H. Tsang...............................................1978 D. A. Antoniadis.......................................1978 D. Y. Wang...............................................1979 C. W. Magee.............................................1979 E. Takayama.............................................1980 H. Reller...................................................1980 W. J. P. Van Enckevort..............................1981 M. W. M. Graef.........................................1981 C. Y. Chao................................................1981 L. F. Lin....................................................1981 D. W. Sittari..............................................1982 T. P. Chow................................................1982 P. G. Pickup..............................................1983 K. F. Jensen..............................................1983 D. B. Graves.............................................1983 N. A. Godshall..........................................1984 E. K. Broadbent........................................1984 J. C. Farmer.............................................1985 G. S. Oehrlein...........................................1985 J. Richer...................................................1986 T. Tanaka..................................................1986 C. P. Wilde................................................1987 P. N. Bartlett.............................................1987 J. Maier....................................................1987 J. A. Bardwell...........................................1988 C.-J. Han..................................................1988 A. E. Husser.............................................1989 D. H. Craston...........................................1989 J. M. Rosamilia........................................1989 J. H. Comfort...........................................1989 M. W. Verbrugge......................................1990 C. J. Giunta..............................................1990 T. J. Mountziaris.......................................1991 J. V. Cole..................................................1991 D. W. Suggs.............................................1991 B. W. Gregory...........................................1991 D. B. Bonham...........................................1992 E. S. Aydil.................................................1992 P. P. Apte..................................................1993 A. West....................................................1993 H. A. Gasteiger.........................................1994 F. R. Myers...............................................1994 R. Vidal....................................................1995 G. D. Papasouliotis...................................1995 J. H. Nordlien...........................................1996 J. Lee.......................................................1996 A. K. Padhi...............................................1997 S. M. Han.................................................1997 A. D. Robertson.......................................1998 Y. Shao-Horn............................................1998 S. R. Kaluri...............................................1998 A. Bautista................................................1999 P. A. O’Neil...............................................1999 R. T. Leah.................................................2000 J. W. Klaus...............................................2000 J. F. Whitacre...........................................2001 P. Feichtinger...........................................2001 T. J. Pricer................................................2002 P. S. Lee...................................................2002

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

K. Jambunathan.......................................2003 S. Noda....................................................2003 M. Miyamoto............................................2003 R. Akolkar................................................2004 Y.-K. Hong................................................2004 S. Borini...................................................2005 M. Kunimatsu...........................................2005 Mathieu Bervas........................................2006 Pradeep Dixit............................................2006 Steffen Eccarius.......................................2007 A. T. J. van Niftrik.....................................2007 Kevin Ralston...........................................2008 Eu Jin Tan................................................2008 Yudi Setiawan..........................................2008 Paul Albertus............................................2009 Louis Hutin..............................................2009 Gijs Dingemans........................................2010 Erik Langereis..........................................2010 Stephen E. Potts......................................2010 Xingbao Zhu.............................................2010 Igor Volov................................................2011 Claudia Fleischmann................................2011 Sebastien Couet.......................................2011 Koen Schouteden.....................................2011 Philipp Hönicke........................................2011 Kiersten Horning......................................2012 Sykes Mason ...........................................2012 Balavinayagam Ramalingam....................2012 Rahul Malik..............................................2013 Aziz Abdellahi...........................................2013 Nathaniel D. Leonard................................2014 Trevor M. Braun.......................................2015

Bruce Deal & Andy Grove Young Author Award Konstantinos Spyrou................................2013 Pengfei Guo.............................................2014 Ran Cheng...............................................2014 Wei Wang.................................................2014 Kohei Shima.............................................2015

ECS General Society Student Poster Session Awards F. Forouzan...............................................1993 D. L. Taylor...............................................1993 L. Abraham..............................................1994 A. J. Aldykiewicz......................................1994 A. Dalmia.................................................1994 M. Murthy................................................1994 R. Munkundan.........................................1995 A. E. Thomas............................................1995 C. E. Ramberg..........................................1995 W. Wang..................................................1995 S. Chen....................................................1996 K. Kowal...................................................1996 C. Leger...................................................1997 E. Potteau.................................................1997 K. Bera.....................................................1998 E. Dickenson............................................1998 G. Q. Lu....................................................1998 M. W. Riley...............................................1998 J. Pearton.................................................1999 89

2015 Y e a r in RE vie w ECS General Society Student Poster Session Awards (continued)

A. Templeson...........................................1999 N. Baydokhi..............................................2000 A. Pismenny.............................................2000 A. Besing..................................................2001 V. Sochnikov............................................2001 S. Dimovski..............................................2002 P. Maitra...................................................2002 H. Ohtsuka...............................................2002 T. Wiley....................................................2002 P. Kavanagh.............................................2003 B. Monahan..............................................2003 O. Rabin...................................................2003 P. Scopece...............................................2003 K. Yasuda.................................................2003 M. Guan...................................................2004 K. Kanaizuka.............................................2004 A. Oide.....................................................2004 R. M. Todi................................................2004 W. J. Cheong............................................2005 J. Chmiola................................................2005 S. Chrisanti..............................................2005 C. Drake...................................................2005 D. L. Gonzalez-Parra................................2006 Naoko Kamiura........................................2006 T. Takeyasu...............................................2006 Arun Vijayakumar.....................................2006 Naoaki Hashimoto....................................2007 Daisuke Kikutani......................................2007 Toyoki Okumura.......................................2007 Gholamreza Rostamikia...........................2007 Arun Vijayakumar.....................................2007 Rajwant Singh Bedi..................................2008 Bryan K. Boggs........................................2008 John Chmiola...........................................2008 Yuta Ishigami...........................................2008 J. S. O’Brien.............................................2008 Tyler Osborn............................................2008 Ralf Peipmann..........................................2008 Philippe Perret.........................................2008 Kenji Takada.............................................2008 Vinit Todi..................................................2008 Natalia B. Shustova..................................2008 Joshua Snyder.........................................2008 Tomomasa Sugiyama...............................2008 Anasuya Adibhatla....................................2009 Magdalena Gizowska................................2009 Frederik Golks..........................................2009 Karina Kangas..........................................2009 Kiera A. Kurak..........................................2009 Manale Maalouf........................................2009 Debasish Mohanty...................................2009 Natalia Shustova......................................2009 Joko Sutrisno...........................................2009 Jaroslaw Syzdek......................................2009 Alex Avekians...........................................2010 Shayna Brocato........................................2010 Pablo de la Iglesia....................................2010 Christian Desilets.....................................2010 Ayesha Maria Hashambhoy......................2010 Carolin Lau...............................................2010

Raja S. Mannam.......................................2010 Joshua P. McClure...................................2010 Sarvesh Pasem........................................2010 Robert Sacci............................................2010 Misato Tashiro.........................................2010 Jesse Benck.............................................2011 Benjamin Caire.........................................2011 Zhebo Chen..............................................2011 Damilola Daramola...................................2011 Kirsten Marie Jensen...............................2011 Javed Khan..............................................2011 Simon Lux................................................2011 Ashley Maes.............................................2011 Lingchong Mai.........................................2011 Francis Richey..........................................2011 Neil Spinner.............................................2011 Melissa Vandiver......................................2011 Georgi Bodurov........................................2012 Aurelien Etiemble ....................................2012 Kiersten Horning .....................................2012 Yoon Jang Kim.........................................2012 Prabhu Doss Mani...................................2012 K. Sykes Mason.......................................2012 Seungha Oh.............................................2012 Michael Siedlik.........................................2012 Bong Seob Yang......................................2012 Yoshinobu Adachi....................................2012 Kwi Nam Han...........................................2012 Takashi Hasegawa....................................2012 Cheng Ai Li...............................................2012 Shigeta Yagyu..........................................2012 Michal Osiak............................................2013 Andrew J. Naylor......................................2013 Danielle Smiley........................................2013 Mohammed Boota....................................2013 Kelsey B. Hatzall.......................................2013 Christopher R. Dennison..........................2013 Tobias Placke...........................................2013 Buido Schmuelling...................................2013 Richard Kloepsch.....................................2013 Olga Fromm.............................................2013 Sergej Rothermel.....................................2013 Paul Meister.............................................2013 Kristy Jost................................................2013 John McDonough....................................2013 Takashi Tsuda...........................................2013 Masanari Hashimoto................................2013 Axel Gambou-Bosca.................................2014 Miguel Angel Arellano Gonzalez...............2014 Andrew Durney........................................2014 Elizabeth Hotvedt.....................................2014 Andrew R. Akbashev................................2014 Jorge Ivan Aldana-Gonzalez.....................2014 Heather Barkholtz.....................................2015 Subrahmanyam Goriparti.........................2015 Daiki Ito....................................................2015 Jonathan Kucharyson..............................2015 Maria Lukatskaya.....................................2015 Kenta Machida.........................................2015 Rajankumar Patel.....................................2015 Xiaoxing Xia.............................................2015

90

ECS Sponsored Meeting Student Poster Award Winners Simposio Brasileiro de Electroquimica e Eletroanalitica (SIBEE) L. M. Nunes.............................................2009 Felipe Ibanhi Pires....................................2011 V. Dos Santos...........................................2013 China Semiconductor Technology International Conference (CSTIC) C. Santini.................................................2009 L. Ma........................................................2010 M. B. Gonzalez.........................................2011 Chien Chi Chen.........................................2012 Tao Deng..................................................2013 Meng Lin..................................................2014 Jin Jisong................................................2015 Xiaofei Wu................................................2015 Yanfen Xiao..............................................2015 Euro CVD Award A. Szkudlarek...........................................2011 Not Awarded............................................2013 IC4N: From Nanoparticles and Nanomaterials to Nanodevices and Nanosystems M. Gharbi.................................................2009 H. N. Green..............................................2011 Mariana Sendova.....................................2013 Sociedad Mexicana de Electroquímica (SMEQ) and ECS Mexican Section Meeting A. Mendez-Albores...................................2008 L. S. Hernandez-Munoz............................2009 C. Avila-Gonzalez.....................................2010 D. C. Martinez-Casillas.............................2011 Lidia G. Trujano-Ortiz...............................2012 Paola Yamela De la Cruz-Guzmán............2013 Maria Dámaris Cortez Diaz.......................2015

Turner Book Prize

S. Speil.....................................................1942 W. G. Berl.................................................1943 J. P. Coyle................................................1944 J. T. Waber...............................................1945 B. Cartwright............................................1946 A. E. Hardy...............................................1947 M. A. Streicher.........................................1948 R. E. Hoeckelman.....................................1949 P. Delahay................................................1950 K. H. Stern...............................................1951 C. C. Templeton........................................1951 P. T. Gilbert...............................................1952 R. B. Holden.............................................1953 D. A. Vermilyea........................................1954 J. G. Jewell...............................................1955 J. H. Westbrook.......................................1956 A. C. Makrides..........................................1957 J. P. Pemsler............................................1958 R. G. Carlson............................................1959 R. E. Meyer..............................................1960 P. C. Milner...............................................1960 H. Freitag.................................................1961 P. J. Boddy...............................................1962

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

2015 Y e a r in Re vie w Turner Book Prize

(continued)

E. J. Cairns...............................................1963 M. Weinstein............................................1963 R. W. Bartlett............................................1964 E. M. Hofer...............................................1965 C. S. Tedmon, Jr.......................................1966 F. P. Kober................................................1967 J. M. Hale.................................................1968

Leadership Circle Awards Legacy Level Dow Chemical Co., Central Research, received 2011 Olin Chlor Alkali Products Division, received 2011 Occidental Chemical Corp., received 2013 Energizer, received 2015 Medallion Level Occidental Chemical Corp., received 2007 Atotech USA, Inc., received 2009 Energizer, received 2009 Diamond Level General Electric Co., Corporate Research & Development, received 2001 General Motors Research Laboratories, received 2001 Rayovac, received 2002 Duracell, received 2006 IBM Corporation, received 2006 Gold Level Toshiba Corp., Research & Development Center, received 1998 Siltronic AG, received 1998 Osram Sylvania, Inc., Chemical & Metallurgical Division, received 1999 Sandia National Laboratories, received 2000 International Lead Zinc Research Organization, Inc., received 2003 Medtronic, Inc., Energy and Component Center, received 2004 Toyota Central Research and Development Labs, Inc., received 2004 Yuasa Corp, received 2004 Princeton Applied Research/Solartron Analytical, received 2005 Saft Batteries, received 2006 CSIRO Minerals, received 2007 Industrie de Nora, received 2007 Ballard Power Systems, Inc., received 2008 ECO Energy Conversion, received 2008 Varta Automotive GmbH, Advanced Battery Division, received 2008 Greatbatch, Inc., received 2010 Leclanche S. A., received 2009 Max-Planck-Institut für Festkörperforschung, received 2009 Giner, Inc., received 2010 Greatbatch, Inc., received 2010 TIMCAL Graphite and Carbon Ltd., received 2011 3M Company, received 2014

Silver Level Eltech Systems Corp., received 1992 Tronox LLC, received 1994 Japan Storage Battery Co., Ltd., received 1997 3M Company, received 1998 E. I. Du Pont de Nemours & Co., Inc., HD Microsystems, received 1998 Solartron Instruments, received 1999 Central Electrochemical Research Institute, received 2002 TDK Corp., R&D Center, received 2002 Valence Technology, received 2002 DAISO, Co., Ltd., received 2003 Panasonic Corp., received 2003 C. Uyemura & Co., Ltd., Central Research Lab, received 2005 Electrosynthesis Co., Inc., received 2005 FMC Corporation, Active Oxidants Division, received 2005 Nacional de Grafite, LTDA, received 2005 Permelec Electrode, Ltd., received 2005 PG Industries, Inc., Chemicals Group Technical Center, received 2005 Scribner Associates, Inc., received 2005 Technic Inc., received 2005 Advance Research Chemicals, Inc., received 2007 Yeager Center for Electrochemical Sciences at CWRU, received 2007 PEC North America, received 2009 Quallion, LLC, received 2009 UTC Power, received 2009 Broddarp of Nevada, received 2010 Teledyne Energy Systems, Inc., received 2010 OM Group, Inc., received 2012 Evonik Degussa GmbH, received 2013 Permascand AB, received 2013 ZSW, received 2014 Lawrence Berkeley National Lab, received 2014 Bronze Level Hach Company, Radiometer Analytical Division, received 2002 De Nora Technologie Elettrochimiche S.r.L., received 2003 BAE Systems Battery Technology Center, received 2005 Agilent Laboratories, received 2008 Evonik Degussa GmbH, received 2008 Samsung SDI, received 2008 GAIA-Akkumulatorenwerke GmbH, received 2009 Permascand AB, received 2009 ZSW Center for Solar Energy & Hydrogen Research, received 2009 Coolohm, Inc., received 2010 ElectroChem, Inc., received 2010 Faraday Technology, Inc., received 2010 Johnson Matthey, received 2010 Metrohm USA, received 2010 Pine Research Instrumentation, received 2010 Sanyo Electric Co. Ltd., received 2011 Nissan Motor Co. Ltd., received 2011 Hydro-Québec, received 2011 Bio-Logic USA/Bio-Logic SAS, received 2012

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

Gamry Instruments, received 2012 Rockwood Lithium, received 2012 ENEOS CELLTECH Co. Ltd., received 2012 Fortu Research GmbH, received 2012 Asahi Kasei E-Materials Corp., received 2014 Gelest, Inc., received 2014 Honda R+D Co. Ltd., received 2014 Next Energy EWE-Forschungszentrum, received 2014 Los Alamos National Laboratory, received 2015 Toyota Research Institute of North America, received 2015

Battery Division Student Research Award

J. R. Waggoner........................................1980 K. E. Yee...................................................1980 W. A. van Schalkwijk................................1981 C. Y. Mak..................................................1986 T. I. Evans................................................1987 C. C. Streinz.............................................1988 J. Weidner................................................1989 M. G. Lee.................................................1990 E. J. Podlaha............................................1991 G. E. Gray.................................................1992 D. Qu........................................................1993 P. De Vidts................................................1994 S. Motupally.............................................1995 J. Xu.........................................................1996 Y. Shao-Horn............................................1997 I. Courtney...............................................1998 G.E. Rousse.............................................1999 V. Srinivasan............................................2000 M. Zhao....................................................2001 V. Subramaniam.......................................2001 L. Fransson..............................................2002 K.-W. Park................................................2003 A. Weber..................................................2004 C. Delacourt.............................................2005 K. Kang....................................................2006 Feng Jiao..................................................2007 Nonglak Meethong...................................2009 Yi-Chun Lu...............................................2010 Christopher Fell........................................2011 Yuhui Chen...............................................2012 Mohammed Ati........................................2013 Martin Ebner............................................2014 Matteo Bianchini......................................2015

Battery Division Research Award

J. J. Lander..............................................1958 D. M. Smyth.............................................1959 T. P. Dirkse...............................................1962 F. G. Will...................................................1964 J. Burbank................................................1966 C. P. Wales...............................................1966 D. Tuomi..................................................1968 Y. Okinaka................................................1970 A. C. Simon .............................................1972 91

2015 Y e a r in RE vie w Battery Division Research Award (continued)

S. M. Caulder...........................................1972 J. McBreen...............................................1974 T. Katan....................................................1976 S. Szpak...................................................1976 A. Heller...................................................1978 K. R. Bullock............................................1980 R. A. Huggins...........................................1982 D. Pavlov..................................................1984 G. H. J. Broers.........................................1985 J. L. Devitt................................................1986 D. H. McClelland......................................1986 J. P. Gabano.............................................1987 M. Armand...............................................1988 J. Jorne....................................................1989 A. N. Dey..................................................1990 R. E. White...............................................1991 D. N. Bennion...........................................1992 E. Peled....................................................1993 K. M. Abraham.........................................1995 J. Dahn.....................................................1996 B. Scrosati...............................................1997 C. Delmas.................................................1999 J. B. Bates................................................2000 S. Wittingham..........................................2002 K. Kinoshita..............................................2003 J. Newman...............................................2004 G. Ceder...................................................2004 M. Thackeray...........................................2005 T. Ohzuku.................................................2006 Clare P. Grey............................................2007 Peter G. Bruce..........................................2008 Linda Nazar..............................................2009 Dominique Guyomard..............................2010 Yang-Kook Sun........................................2011 Stefano Passerini.....................................2012 Doron Aurbach.........................................2013 Arumugam Manthiram.............................2014 Martin Winter...........................................2015

Battery Division Technology Award Y. Nishi.....................................................1994 K. Ozawa..................................................1994 E. S. Takeuchi...........................................1995 S. Gilman.................................................1996 J.-M. Tarascon.........................................1997 G. E. Blomgren.........................................1998 A. Yoshino................................................1999 H. Y. Cheh................................................2000 B. B. Owens.............................................2001 D. Wilkinson.............................................2002 M. Winter.................................................2002 J. Yamaki.................................................2003 M. Yoshio.................................................2003 M. Ue.......................................................2004 D. Aurbach...............................................2005 P. Novak...................................................2005 K. Lee.......................................................2006 Michel Broussely......................................2007 Hiroshi Inoue...........................................2008 Satoshi Mizutani......................................2008

Eiji Endoh.................................................2009 Khalil Amine.............................................2010 Jeffrey Dahn.............................................2011 Yet-Ming Chiang.......................................... 2012 Karim Zaghib................................................ 2013 Feng Wu....................................................... 2014 Ashok Shukla............................................... 2015

Corrosion Division H. H. Uhlig Award

Q. Meng...................................................2004 D. Chidambaram......................................2005 H. Tsuchiya..............................................2006 Magnus Johnson.....................................2007 Christopher D. Taylor...............................2008 Mariano Iannuzzi......................................2009 Pouria Ghods...........................................2010 Hongbo Cong...........................................2011 Mariano Kappes.......................................2012 Quentin Van Overmeere...........................2013 Yolanda Hedberg......................................2014 Eric Schindelholz......................................2015

(formerly the Outstanding Achievement Award of the Corrosion Division 1973-1983)

M. Cohen.................................................1973 D. A. Vermilyea........................................1975 J. Kruger..................................................1977 M. J. Pryor...............................................1979 T. R. Beck.................................................1981 N. Sato.....................................................1983 P. Kofstad.................................................1985 H. W. Pickering........................................1987 R. P. Frankenthal......................................1989 H. Leidheiser............................................1991 H. Isaacs..................................................1993 W. H. Smyrl..............................................1995 M. J. Graham...........................................1997 K. Hashimoto...........................................1999 D. Macdonald...........................................2001 F. Mansfeld...............................................2002 C. Leygraf.................................................2003 R. Newman..............................................2004 P. Marcus.................................................2005 G. T. Burstein...........................................2006 Edward McCafferty...................................2007 Martin Stratmann.....................................2008 John R. Scully..........................................2009 Gerald S. Frankel......................................2010 Patrik Schmuki.........................................2011 Hans-Henning Strehblow.........................2012 Mário Ferreira..........................................2013 Paul Natishan...........................................2014 David Shoesmith......................................2015

Corrosion Division Morris Cohen Graduate Student Award (formerly the Corrosion Division Award for Summer Study 1986-1988)

S. D. Scarberry........................................1986 C. C. Streinz.............................................1987 R. Bianco.................................................1988 M. A. Harper.............................................1992 R. G. Buchheit..........................................1993 J.-F. Yan...................................................1994 B. V. Cockeram.........................................1995 I. Odnevall................................................1996 D. G. Kolman............................................1997 C. S. Brossia............................................1998 M. Verhoff................................................1999 S. Yu........................................................2000 S. F. Nitodas.............................................2001 K. Cooper.................................................2002 T. Ramgopal.............................................2003

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Dielectric Science and Technology Division Thomas D. Callinan Award J. A. Davies..............................................1968 J. P. S. Pringle..........................................1968 G. M. Sessler...........................................1970 J. E. West.................................................1970 C. A. Mead...............................................1971 W. Kern....................................................1972 J. R. Szedon.............................................1973 C. M. Osburn............................................1975 T. W. Hickmott..........................................1976 J. R. Ligenza............................................1977 R. Williams...............................................1978 R. J. Kriegler............................................1979 B. E. Deal.................................................1982 L. Young..................................................1983 A. K. Sinha...............................................1985 A. C. Adams.............................................1986 S. P. Murarka...........................................1987 R. B. Comizzoli.........................................1988 E. A. Irene................................................1988 R. A. Levy.................................................1989 M. H. Woods............................................1990 V. J. Kapoor..............................................1991 S. I. Raider...............................................1992 D. W. Hess...............................................1993 Y.-H. Wong...............................................1994 K. L. Mittal...............................................1995 W. D. Brown.............................................1996 J. P. Dismukes.........................................1997 R. Singh...................................................1998 A. Rohatgi................................................1999 K. Saraswat..............................................2000 P. Ho........................................................2001 J. Deen.....................................................2002 S. K. Banerjee...........................................2003 A. G. Revesz.............................................2003 S. Fonash.................................................2004 Paul A. Kohl.............................................2008 Tsu-Jae King Liu......................................2011 Durgamadhab (Durga) Misra...................2013 Kalpathy Sundaram..................................2015

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2015 Y e a r in Re vie w

Electrodeposition Division Research Award W. Weil.....................................................1980 Y. Okinaka................................................1981 E. B. Budevski..........................................1982 R. C. Alkire...............................................1983 L. T. Romankiw........................................1984 R. J. von Gutfeld......................................1984 J. W. Dini.................................................1985 H. R. Johnson..........................................1985 H. Leidheiser............................................1986 J. P. Hoare................................................1987 H. Y. Cheh................................................1988 D. S. Lashmore........................................1989 S. Nakahara..............................................1990 T. C. Franklin............................................1991 R. E. White...............................................1992 P. C. Andricacos.......................................1993 M. J. Froment...........................................1994 D. Landolt................................................1995 T. Osaka...................................................1996 M. Schlesinger.........................................1997 Madhav Datta...........................................1998 R. Winand................................................1999 H. Honma.................................................2000 D. Kolb.....................................................2002 J. Switzer.................................................2003 J. Dukovic................................................2004 P. Bartlett.................................................2005 T. P. Moffat.............................................. 2006 Ibro Tabakovic..........................................2007 Olaf Magnussen.......................................2008 John Stickney..........................................2009 Takayuki Homma......................................2010 Philippe Allongue.....................................2011 Hariklia Deligianni....................................2012 Daniel Lincot............................................2013 Alan C. West............................................2014 Daniel Schwartz.......................................2015

Electronics and Photonics Division Award F. A. Trumbore..........................................1970 F. C. Palilla................................................1971 M. B. Panish.............................................1972 W. A. Pliskin.............................................1973 B. E. Deal.................................................1974 H. M. Manasevit.......................................1975 M. G. Craford...........................................1976 A. Y. Cho..................................................1977 C. M. Wolfe..............................................1978 E. Sirtl......................................................1979 J. M. Woodall...........................................1980 G. A. Rozgonyi.........................................1981

G. W. Cullen.............................................1982 D. W. Shaw..............................................1983 A. Reisman...............................................1984 S-M. Hu...................................................1985 E. H. Nicollian...........................................1986 B. Schwartz..............................................1987 K. E. Bean.................................................1988 T. Kamins.................................................1989 D. M. Brown.............................................1990 C. M. Osburn............................................1991 G. S. Oehrlein...........................................1992 B. S. Meyerson.........................................1993 G. K. Celler...............................................1994 L. C. Kimerling.........................................1995 H. Huff.....................................................1996 A. F. Tasch................................................1997 U. M. Gösele............................................1999 S. N. G. Chu.............................................2000 S. P. Murarka...........................................2001 S. Cristoloveanu.......................................2002 T. Ohmi....................................................2003 C. Claeys..................................................2004 S. Pearton................................................2005 H. Massoud..............................................2006 Yue Kuo...................................................2007 Fan Ren....................................................2008 Eicke R. Weber.........................................2009 Lih J. Chen...............................................2010 M. Jamal Deen.........................................2011 Chennupati Jagadish ...............................2012 Durgamadhab (Durga) Misra...................2013 Albert Baca...............................................2014 Cammy Abernathy....................................2015

Energy Technology Division Research Award M. W. Verbrugge......................................1994 S. Srinivasan............................................1996 H. R. Kunz................................................1998 A. W. Czanderna.......................................1999 R. Selman................................................2001 I. Uchida...................................................2001 A. Nozik....................................................2003 K. Kinoshita..............................................2004 K. Kanamura............................................2005 S. Licht.....................................................2006 Radoslav Adzic.........................................2007 Yang Kook Sun........................................2007 Tom Fuller................................................2008 Krishnan Rajeshwar.................................2009 Jai Prakash..............................................2009 John Weidner...........................................2010 Karim Zaghib............................................2010 Claude Levy-Clément...............................2011 Piotr Zelenay............................................2013 James Fenton...........................................2014 Rodney Borup..........................................2015

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

Energy Technology Division Srinivasan Young Investigator Award Vijay Ramani............................................2012 Adam Weber............................................2012 Stefan Freunberger..................................2013 Minhua Shao............................................2014 William Mustain.......................................2015

Energy Technology Division Graduate Student Award Thomas Dursch........................................2014 James Radich..........................................2014 Scott Cushing..........................................2015 Haegyeom Kim.........................................2015

High Temperature Materials Division Outstanding Achievement Award J. B. Wagner, Jr........................................1986 W. L. Worrell............................................1988 R. A. Rapp................................................1990 H. Schmalzried.........................................1992 S. C. Singhal............................................1994 C. G. Vayenas...........................................1996 C. Bernard................................................2001 H. Yokokawa............................................2002 K. Spear...................................................2004 A. Virkar...................................................2006 David J. Young.........................................2008 Harry L. Tuller..........................................2010 Eric Wachsman........................................2012 Janusz Nowotny.......................................2014

High Temperature Materials Division J. B. Wagner, Jr. Young Investigator Award S. Mohney................................................1999 S. M. Haile...............................................2001 M. Swihart...............................................2003 R. Mukundan...........................................2005 Xiao-Dong Zhou.......................................2007 Juan Claudio Nino....................................2009 Toshiaki Matsui........................................2011 Paul Gannon............................................2013

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Industrial Electrochemistry and Electrochemical Engineering Division New Electrochemical Technology (NET) Award Asahi Glass Company..............................1999 DeNora Tecnologie...................................2005 E-Tek........................................................2005 Bayer Material Science AG.......................2005 Ballard Power Systems............................2007 FuelCell Energy........................................2009 U.S. Army Engineer Research and Development Center, Construction Engineering Research Laboratory, and Electro Tech CP........................................2011 UTC Power...............................................2013 Matthew Ward Brodt................................2014 Proton OnSite..........................................2015

Industrial Electrochemistry and Electrochemical Engineering Division H. H. Dow Memorial Student Achievement Award R. Bakshi..................................................1991 G. J. Yusem..............................................1992 J. A. Poirier..............................................1993 S. Siu.......................................................1994 M. Vreeke.................................................1995 A. E. Thomas............................................1996 S. A. Leith................................................1997 P. Soo.......................................................1998 S. Sriramulu.............................................1999 K. M. Jeerage...........................................2000 A. L. Prieto...............................................2001 W. He.......................................................2002 J. Zhang...................................................2003 S. Basker..................................................2004 V. Ramani.................................................2005 N. Jalani...................................................2006 Brenda L. Garcia-Diaz..............................2007 Sunil Roy.................................................2008 Prabeer Barpanda....................................2009 Brandon Bartling......................................2010 Long Cai...................................................2011 Meng Li....................................................2012 Young Woo-Lee.......................................2013 Matthew Ward Brodt................................2014 Santosh Vijapu.........................................2015

Industrial Electrochemistry and Electrochemical Engineering Division Student Achievement Award Y.-E. Sung................................................1995 J. K. N. Mbindyo......................................1996

C. A. Smith...............................................1997 J. A. Drake...............................................1998 R. Lowrey.................................................1999 C. Arvin....................................................2000 B. Djurfors...............................................2001 V. Subramanian........................................2002 P. M. Gomadam.......................................2003 I. AlNashef...............................................2004 V. Sethuraman..........................................2006 Minhua Shao............................................2007 Vinten Dewikar.........................................2008 Paul Albertus............................................2009 Satheesh Sambandam.............................2010 Venkatasailanathan Ramadesigan............2011 Rainer Kungas..........................................2012 Wei Yan....................................................2013 Christopher Arges....................................2013 Paul Northrop..........................................2014 Venkata Raviteja Yarlagadda....................2014 Vedasri Vedharathinam............................2014 Mohammad Mahdi Hasani-Sadrabadi......2015

Luminescence and Display Materials Division Centennial Award A. Meijerink..............................................2004 A. Srivastava............................................2004 H. Guedel.................................................2006 David J. Lockwood...................................2010 Hajime Yamamoto....................................2012

Nanocarbons Division Richard E. Smalley Research Award Sumio Ijima..............................................2008 Phaedon Avouris......................................2009 Robert Haddon.........................................2011 Nazario Martín..........................................2013 Dirk Guldi.................................................2015

SES Research Young Investigator Award of the Nanocarbons Division Nikhil Koratkar.........................................2009 Mark C. Hersam.......................................2010 Aurelio Mateo-Alonso..............................2012

S. Torii.....................................................1998 J. Simonet................................................2000 J. Utley.....................................................2000 J. M. Savéant...........................................2002 M. Tokuda................................................2004 D. Evans...................................................2004 I. Nishiguchi.............................................2006 Albert Fry.................................................2008 Toshio Fuchigami.....................................2010 Dennis Peters...........................................2012 Jun-Ichi Yoshida......................................2014

Physical and Analytical Electrochemistry Division David C. Grahame Award F. C. Anson...............................................1983 J. Newman...............................................1985 A. Heller...................................................1987 M. J. Weaver............................................1989 B. Miller...................................................1991 A. T. Hubbard...........................................1993 R. M. Wightman.......................................1995 D. M. Kolb................................................1997 P. N. Ross, Jr............................................1999 D. A. Scherson.........................................2001 A. Wieckowski..........................................2003 H. White...................................................2005 Joseph T. Hupp........................................2007 Héctor D. Abruña.....................................2009 Masatoshi Osawa.....................................2011 Richard L. McCreery................................2013 Hubert Gasteiger......................................2015

Physical and Analytical Electrochemistry Division Max Bredig Award in Molten Salt Chemistry M. Blander...............................................1987 G. P. Smith..............................................1990 R. A. Osteryoung......................................1992 G. Mamantov...........................................1994 N. Bjerrum...............................................1996 H. A. Øye..................................................1998 Y. Ito........................................................1999 G. N. Papatheodorou................................2002 M. Gaune-Escard.....................................2004 J. Wilkes..................................................2006 Bernard Gilbert.........................................2008 C. Austen Angell.......................................2010 Derek Fray................................................2012 Charles Hussey........................................2014

Organic and Biological Electrochemistry Division Manuel Baizer Memorial Award T. Shono...................................................1994 H. Lund....................................................1996 H. Schäfer................................................1998

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2015 Y e a r in Re vie w Canada Section Electrochemical Award Sensor Division Outstanding Achievement Award J. Janata...................................................1994 R. P. Buck.................................................1996 I. Lundström............................................1998 A. J. Ricco................................................2000 M. Aizawa.................................................2002 N. Yamazoe..............................................2004 W. Heineman............................................2006 Chung-Chiun Liu......................................2008 Thomas Thundat......................................2010 Sheikh Ali Akbar.......................................2012 Peter Hesketh...........................................2014

E. J. Casey...............................................1982 Brian E. Conway.......................................1986 L. Young..................................................1990 S. Flengas................................................1994 Jacek Lipkowski.......................................1998 Jean Lessard............................................2002 Jeffrey R. Dahn........................................2006 David Shoesmith......................................2010

Canada Section R. C. Jacobsen Award George Fraser..........................................1988 Barry MacDougall....................................1990 Louis Brossard.........................................1994 Ernest E. Criddle......................................2002 Sharon G. Roscoe....................................2006 Jacek Lipkowski.......................................2010

Canada Section W. Lash Miller Award Sensor Division Student Paper Award Jeffrey Kirsch...........................................2012 Kazuaki Edagawa......................................2012

Gwendolyn B. Wood Section Excellence Award Metropolitan New York Section...... 1975-1976 Columbus Section.......................... 1976-1977 Chicago Section............................. 1979-1980 Chicago Section............................. 1980-1981 Chicago Section............................. 1981-1982 Southern Wisconsin Section.......... 1982-1983 Southern Wisconsin Section.......... 1983-1984 Southern Wisconsin Section.......... 1984-1985 National Capital Section................. 1985-1986 North Texas Section....................... 1986-1987 Southern Wisconsin Section.......... 1987-1988 Chicago Section............................. 1988-1989 Southern Wisconsin Section.......... 1989-1990 North Texas Section....................... 1990-1991 Southern Wisconsin Section.......... 1991-1992 Southern Wisconsin Section.......... 1992-1993 New England Section..................... 1993-1994 National Capital Section................. 1994-1995 National Capital Section................. 1995-1996 National Capital Section................. 1996-1997 Canadian Section and National Capital Section................. 1997-1998 Chicago Section............................. 1998-1999 New England Section..................... 1999-2000 National Capital and New England Section..................... 2000-2001 National Capital Section................. 2001-2002 National Capital Section................. 2002-2003 San Francisco Section.................... 2003-2004 San Francisco Section.................... 2004-2005 San Francisco Section.................... 2005-2006

J. L. Ord...................................................1969 J. E. Desnoyers........................................1971 A. K. Vijh..................................................1973 W. R. Fawcett...........................................1975 W. A. Adams, A. J. Spring Thorpe............1977 Barry MacDougall....................................1979 David W. Shoesmith.................................1981 A. Belanger...............................................1983 Viola I. Birss.............................................1985 S. Das Gupta............................................1987 K. Tomantscher, D. Leaist........................1989 Jennifer Bardwell.....................................1991 Jeff Dahn..................................................1993 Alireza Zolfaghari-Hesari..........................1999 Daniel Bizzotto.........................................2001 Jamie Noel...............................................2003 Aicheng Chen...........................................2009 Hua-Zhong (Hogan) Yu............................2011 Not Awarded............................................2013 Federico Rosei.........................................2015

Canada Section Student Award Jean St-Pierre..........................................1988 Gessie Brisard..........................................1989 James Hinatsu.........................................1990 Gregory Jerkiewicz...................................1991 Hubert Dumont........................................1992 Meijie Zhang............................................1993 Dan Bizzoto..............................................1994 Sylvie Morin.............................................1995 Alexandre Brolo........................................1996 Aicheng Chen...........................................1997 Ian A. Courtney........................................1998 Dany Brouillette........................................1999 Shiyuan Qian............................................1999 Bryan Park...............................................2000 Luc Beaulieu............................................2001 Vlad Zamliny............................................2002 Sandra Rifai.............................................2003 Amy Lloyd................................................2004 M. Toupin.................................................2006

The Electrochemical Society Interface • Summer 2016 • www.electrochem.org

Thamara Laredo.......................................2007 Arash Shahryari.......................................2008 Mohamed Naser.......................................2009 Mohammed Naser....................................2010 Ahmad Ghahremaninezhad......................2011 Karen Chan..............................................2012 Drew Higgins...........................................2013

Cleveland Section Ernest B. Yeager Electrochemistry Award B. Miller...................................................2004 Richard McCreery....................................2006 Uziel Landau............................................2008 Jacek Lipkowski.......................................2010 Gerald Frankel..........................................2012

Europe Section Gerischer Award Akira Fujishima........................................2003 Michael Graetzel.......................................2005 Allen J. Bard.............................................2007 Rüdiger Memming...................................2009 Helmut Tributsch......................................2011 Arthur Nozik.............................................2013 Adam Heller.............................................2015

Europe Section Alessandra Volta Award M. Armand...............................................2000 J.-M. Tarascon.........................................2002 R. G. Compton.........................................2004 Bruno Scrosati.........................................2006 Not Awarded............................................2010 Jean-Noël Chazalviel................................2012 Phillip Bartlett..........................................2014

Georgia Section Student Award Matthew Lynch.........................................2012 Kara Evanoff.............................................2013 Johanna Karolina Stark............................2014

Korea Section Student Award Ho-Suk Ryu..............................................2006 Jae-Hwan Oh............................................2007 Sung Ki Cho.............................................2008 Cheol-Min Park........................................2009 Ji-Hyung Han...........................................2010 Young Woo Lee........................................2011 Not Awarded............................................2012 Seong Min Bak.........................................2013 Haegyeom Kim.........................................2014 Minah Lee................................................2015

National Capital Section William Blum Award W. Blum...................................................1958 S. Schuldiner...........................................1960 D. N. Craig...............................................1962 A. Brenner................................................1964 J. Kruger..................................................1966 J. Burbank................................................1969 95

2015 Y e a r in RE vie w National Capital Section William Blum Award (continued)

K. H. Stern...............................................1972 B. F. Brown...............................................1974 A. C. Simon..............................................1976 R. T. Foley................................................1978 R. de Levine.............................................1980 E. McCafferty...........................................1982 R. L. Jones...............................................1984 Ugo Bertocci............................................1986 P. J. Moran...............................................1988 M. H. Peterson.........................................1990 D. S. Lashmore........................................1992 J. R. Scully...............................................1994 Paul M. Natishan......................................1996 G. D. Davis...............................................1998 W. E. O'Grady...........................................2000 Thomas P. Moffat.....................................2002 J. L. Hudson.............................................2004

National Capital Section Robert T. Foley Award R. T. Foley................................................1989 W. J. Hamer.............................................1991 G. E. Stoner..............................................1993 P. J. Moran...............................................1995 P. M. Natishan..........................................1997 J. Kruger..................................................1999 R. G. Kelly................................................2001

San Francisco Section Daniel Cubicciotti Student Award L. J. Oblonsky..........................................1995 Y. Ma........................................................1996 C. Wade...................................................1997 C. R. Horne..............................................1998 M. Tucker.................................................1999 L. V. Protsailo...........................................2000 H. Visser..................................................2001 D. Wheeler...............................................2002 J. Hollingsworth.......................................2003 E. Guyer...................................................2004 D. Steingert..............................................2005 Sarah Stewart..........................................2006 James Wilcox...........................................2007 Susan Ambrose........................................2008 Que Anh Nguyen...... Honorable Mention 2008 Yuan Yang ............... Honorable Mention 2008 Paul Albertus............................................2009 Andrew Lee.............. Honorable Mention 2009 Mark Oliver ............. Honorable Mention 2009 Venkat Viswanathan.................................2010 Yi Wei Chen.............. Honorable Mention 2010 Thomas Conry......... Honorable Mention 2010 Maureen Tang..........................................2011 Yi Wei Chen.............. Honorable Mention 2011 Thomas Conry......... Honorable Mention 2011 Allison Engstrom......................................2012

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Matthew McDowell...... Honorable Mention 2012 Xiongwu Kang.......... Honorable Mention 2012 Daniel Cohen............................................2013 Mallory Hammock.... Honorable Mention 2013 Anthony Ferrese....... Honorable Mention 2013 Nian Liu....................................................2014 Isaac Markus............ Honorable Mention 2014 Alan Berger.............. Honorable Mention 2014 Karthish Manthiram.................................2015 Christina Li............... Honorable Mention 2015 Lei Cheng................. Honorable Mention 2015

Outstanding Student Chapter Award University of Maryland.............................2013 Ohio University.....Chapter of Excellence 2013 University of Texas at Austin......Chapter of Excellence 2013 University of Texas at Austin....................2014 University of Maryland...........Chapter of Excellence 2014 Valley of the Sun (Central Arizona)...Chapter of Excellence 2014 Indiana University....................................2015 University of Virginia.............Chapter of Excellence 2015 University of Maryland...........Chapter of Excellence 2015

The Electrochemical Society Interface â&#x20AC;˘ Summer 2016 â&#x20AC;˘ www.electrochem.org

PRiME 2016 October 2 â&#x20AC;&#x201C; 7, 2016 Honolulu, Hawaii

Hawaii Convention Center & Hilton Hawaiian Village

Meeting Topics A - Batteries and Energy Storage

I - Fuel Cells, Electrolyzers, and Energy Conversion

B - Carbon Nanostructures and Devices

J - Luminescence and Display Materials, Devices, and Processing

C - Corrosion Science and Technology

K - Organic and Bioelectrochemistry

D - Dielectric Science and Materials

L - Physical and Analytical Electrochemistry, Electrocatalysis, And Photoelectrochemistry

E - Electrochemical/Electroless Deposition F - Electrochemical Engineering

M - Sensors

G - Electronic Materials and Processing

Z - General Topics

H - Electronic and Photonic Devices and Systems

Important Deadlines Discounted hotel rates starting at $195 at the Hilton Hawaiian Village (the PRiME HQ hotel) and $149 at the Ala Moana Hotel in Honolulu, HI will be available. The reservation deadline for both is September 11, 2016 or until the blocks sell out, so reserve early!

Early-bird pricing is available through September 2, 2016.

Travel grants are available for student attendees and young professional (early career and faculty) attendees.

PRiME 2016 will be held at the Hawaii Convention Center & Hilton Hawaiian Village. Please visit the PRiME webpage for the most up-to-date information on hotel accommodations, registration, short courses, special events, and to review the online technical program. Full papers presented at ECS meetings will be published in ECS Transactions.

PRiME 2016 is the joint international meeting of:

2016 Fall Meeting of The Electrochemical Society of Japan

230th Meeting of The Electrochemical Society

2016 Fall Meeting The Korean Electrochemical Society

with the technical co-sponsoring of: Chinese Society of Electrochemistry

Electrochemistry Division of the Royal Australian Chemical Institute

Korean Physical Society Semiconductor Division

The Japan Society of Applied Physics

Semiconductor Physics Division of Chinese Physics Society

www.PRiME-intl.org