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EMERGING CARBON MATERIALSFOR CATALYSIS EMERGING CARBON MATERIALSFOR CATALYSIS Editedby SAMAHESADJADI
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Dedication Tomyfather,wholovedmeunconditionally;thankstohimforsupporting meashecouldreadmywordsinmysilenceandguidedmebyallthemeans athisdisposal.
Contributors K.S.Adarsh
ElectroplatingMetalFinishingandTechnologyDivision,CSIR-CentralElectrochemical ResearchInstitute,Karaikudi,TamilNadu,India
FranciscoAlcaideMonterrubio CIDETEC,Donostia-SanSebastia ´ n,Spain
C.Alegre
InstitutodeCarboquı´mica,CSIC,Zaragoza,Spain
M.Bernardo
LAQV/REQUIMTE,DepartmentofChemistry,FacultyofScienceandTechnology, NOVAUniversityofLisbon,Caparica,Portugal
NaveenChandrasekaran
ElectroplatingMetalFinishingandTechnologyDivision,CSIR-CentralElectrochemical ResearchInstitute,Karaikudi,TamilNadu,India
CatherineCollett
DepartmentofChemical&BiologicalEngineering,UniversityofSheffield,Sheffield, UnitedKingdom
GarethDavies
DepartmentofChemical&BiologicalEngineering,UniversityofSheffield,Sheffield, UnitedKingdom
C.Dura ´ n-Valle
DepartmentofOrganicandInorganicChemistry,UniversityofExtremadura,Badajoz,Spain
AhmedElSheikh
DepartmentofChemical&BiologicalEngineering,UniversityofSheffield,Sheffield, UnitedKingdom
I.Fonseca
LAQV/REQUIMTE,DepartmentofChemistry,FacultyofScienceandTechnology, NOVAUniversityofLisbon,Caparica,Portugal
JoseM.Fraile
FacultyofSciences,InstituteofChemicalSynthesisandHomogeneousCatalysis(ISQCH), CSIC-UniversityofZaragoza,Zaragoza,Spain
JunkuoGao
InstituteofFiberBasedNewEnergyMaterials,SchoolofMaterialsScienceandEngineering, ZhejiangSci-TechUniversity,Hangzhou,China
GonzaloGarcı ´ a
DepartmentofChemistry,InstituteofMaterialsandNanotechnology,UniversityofLa Laguna,LaLaguna,Tenerife,Spain
EnriqueGarcı´a-Bordeje
InstituteofCarbochemistry(ICB-CSIC),Zaragoza,Spain
GunniyaHariyanandamGunasekar
CleanEnergyResearchCentre,KoreaInstituteofScienceandTechnology,Cheongryang, Seoul,RepublicofKorea
BabakKarimi
DepartmentofChemistry,InstituteforAdvancedStudiesinBasicSciences(IASBS), Zanjan,Iran
M.J.La ´ zaro
InstitutodeCarboquı´mica,CSIC,Zaragoza,Spain
I.Matos
LAQV/REQUIMTE,DepartmentofChemistry,FacultyofScienceandTechnology, NOVAUniversityofLisbon,Caparica,Portugal
E.PerezMayoral
DepartmentofInorganicChemistryandTechnicalChemistry,FacultyofScience,National UniversityofDistanceEducation,UNED,Madrid,Spain
JamesMcGregor
DepartmentofChemical&BiologicalEngineering,UniversityofSheffield,Sheffield, UnitedKingdom
ElenaPastor
DepartmentofChemistry,InstituteofMaterialsandNanotechnology,UniversityofLa Laguna,LaLaguna,Tenerife,Spain
S.Perez-Rodrı ´ guez
InstitutodeCarboquı´mica,CSIC,Zaragoza,Spain
ElisabetPires
FacultyofSciences,InstituteofChemicalSynthesisandHomogeneousCatalysis(ISQCH), CSIC-UniversityofZaragoza,Zaragoza,Spain
SamaheSadjadi
GasConversionDepartment,FacultyofPetrochemicals,IranPolymerandPetrochemical Institute,Tehran,Iran
SodehSadjadi
NuclearScienceandTechnologyResearchInstitute,Tehran,Iran
D.Sebastia ´ n
InstitutodeCarboquı´mica,CSIC,Zaragoza,Spain
YuhangWu
InstituteofOptoelectronicMaterialsandDevices,ChinaJiliangUniversity,Hangzhou, People’sRepublicofChina;InstituteofFiberBasedNewEnergyMaterials,Schoolof MaterialsScienceandEngineering,ZhejiangSci-TechUniversity,Hangzhou,China
HuiXu
InstituteofOptoelectronicMaterialsandDevices,ChinaJiliangUniversity,Hangzhou, People’sRepublicofChina
IbrahimYakub
DepartmentofChemical&BiologicalEngineering,UniversityofSheffield,Sheffield, UnitedKingdom
SunghoYoon
DepartmentofChemistry,Chung-AngUniversity,Dongjak-gu,Seoul,RepublicofKorea
Acknowledgment “ThesupportofIranPolymerandPetrochemicalInstituteisappreciated.”
Newaspectsofcovalenttriazine frameworksinheterogeneous catalysis GunniyaHariyanandamGunasekara andSunghoYoonb
aCleanEnergyResearchCentre,KoreaInstituteofScienceandTechnology,Cheongryang, Seoul,RepublicofKorea
bDepartmentofChemistry,Chung-AngUniversity,Dongjak-gu,Seoul,RepublicofKorea
1Introduction Thecontinuousenvironmentalandeconomicchallengesintheworld stronglyimpulsethechemicalindustriestodevelopsimpleandmoreefficientchemicalprocessesthatutilizeenvironmentallybenigncatalysts,reactants,solvents,andminimumenergyinputstoproduceselectiveproducts withalmostnoorminimalwastes.Todate,mostindustrialchemicalconversions(>90%)usecatalystsatleastinasinglesteptospeedupthereaction rate [1,2],andhenceoneofthemostpromisingstrategywouldbedevelopingeconomicallysimpleandenvironmentallyfriendlyactivecatalyticsystemsforvarioustransformationswithutmost(100%)selectivityand durabilityatminimumenergyinputs.This,ontheotherside,currently drivestheresearchoncatalysisacrosschemistryandchemicalengineering.
Todate,industriesmainlyuse“classic”heterogeneouscatalystsforthe chemicalconversions [3–6],owingtotheirrobustnature,easycatalyst separation,recovery,regenerationandreuse,andtheirfacilepracticalapplicabilityincontinuousoperatingequipmentsystems.However,thesecatalystsusuallyshowlowercatalyticefficiencyandselectivityandusually requireharshreactionconditionsincludinghightemperatureandpressure, etc.Inaddition,thesecatalystsoftenhavemultipleactivesitesinthecatalytic entity,andthus,developingcatalystdesignstrategiesforintroducingspecific activestieswithgreateruniformityisgenerallydifficult.Hence,numerous trial-and-errorexperimentsarehistoricallyrequiredtoproducehighly activeandselectivecatalyticsystems.Suchexperimentshavebeenmainly limitedtoalteringtheparticlesizeofactivemetals,catalystsupportand itsacidity/basicity,theuseofpromotersandalloyformation,etc. [7–9].
Therefore,thedesignanddevelopmentofsingle-sitewell-definedcatalysts thatenablerapidandselectivetransformationwitheasyseparationofcatalyst/productisstillaparamountchallengeinthefieldofcatalysis.
Inthisregard,heterogenizedorimmobilizedcatalystsaregaining increasingattentionacrossthescientificandtechnologicalsocietyowing totheirconceptualviabilityofhavinghighcatalyticactivity,selectivity, finelydistributedandwell-definedactivesingle-sites,andfacilecatalyst handlingandseparation [9–15].Withthisinmind,substantialefforthasbeen focusedtoimmobilizehomogeneouscatalystsontosuitablesolidsupports forprocuringmaximalactivityandstability.Therearefourcommon methodsthatareclassifiedbasedontheinteractionbetweenthecatalyst andthesolidscaffoldfortheheterogenizationofhomogeneouscatalysts ontosolidsupportmaterials:(1)covalentbinding [16–20];(2)electrostatic interaction [21–23];(3)adsorption [24,25];and(4)encapsulation [26–29]. Amongthem,covalentbondingisthemostfrequentlyusedmethodfor theimmobilizationofthehomogeneouscatalysts.Foralongtime,conventionalsolidsupportssuchassilica,zeolite,alumina,polyethyleneglycoland polystyrene,etc.wereappliedtoanchorhomogeneouscomplexes [30–34]. However,theinterestongraftingthecomplexesontheconventionalsolid supportisgraduallyfadingowingtotheirlowstabilityandactivityandhigh cost [35].Themainreasonfortheirlowstabilityistheundesirableinteractionbetweenthesupportscaffoldandthecatalystactivesites,causedfrequentlybytheuseoflinkers.Therefore,theviabilityofimmobilized catalystsinindustrialcatalytictransformationshasbeenquestioned [35] Nevertheless,researchonrealizingthisconceptuallyidealcatalystisstill dynamic,especiallyowingtotherecentemergenceofthermallyandchemicallyrobusthigh-surface-areaporousmaterialsandnovelmethodsforthe immobilization.
Forthepasttwodecades,high-surface-areaporoussolidpolymershave beengainingsignificantinterestacrossdiverseresearchfieldsincludingcatalysis,gascaptureandseparationtechnology,semiconductors,photochemistry,andbiology [36,37].Thesepolymersarebroadlyclassifiedintometal organicframeworks(MOFs)andporousorganicframeworks(POFs). MOFsaregenerallycomposedofinorganicmetalionsorclustersasbuilding unitsandorganicfunctionalgroupsaslinkers,andtheyareconnectedvia coordinationbonds [38–40].POFs,ontheotherhand,aresolelyconstructedfromorganicunitsconnectedviacovalentbonds [41–44].These materialsusuallypossesssurfaceareaintherangefromafewhundredtoseveralthousandsm2 g 1,withuniformandtunableporesizesfrommicro-to
mesopores.Inaddition,awiderangeofchemicalfunctionalities,including organicfunctionalligands,canbeintroducedintheskeletonoftheseframeworks.Generally,MOFsexhibitpoorchemicalstabilityunderharshreactioncondition,suchasunderahighlybasicandacidicsolution,compared toPOFsbecauseoftheirintrinsiccoordinationchemicalbonds [45–48] Ontheotherhand,POFsshowgreaterchemicalstabilitybecauseofthe strongcovalentbondsbetweentheirlightweightelementsandhave,thus, emergedasattractiveandeffectiveporousmaterials,especiallyinthefield ofcatalysis.
DifferenttypesofPOFsthatarecla ssifiedbasedonthestructureof themolecularbuildingblockhavebeendevelopedinrecentyears, includingcovalenttriazineframeworks(CTFs) [49],porousaromatic frameworks(PAFs) [50] ,covalentorganicframeworks(COFs) [51,52], benzimidazole-linkedpolymers(BILPs) [53,54],polymersofintrinsic porosity(PIMs) [55],hyper-cross-linkedpolymers(HCPs) [56,57] ,conjugatedmicroporouspolymers(CMPs) [58,59],andporousiminepolymers(CIFs) [60]
CTFisoneofthemostinterestingclassesofPOFs(Fig.1),receiving intensivelimelightinthefieldofcatalysis.Theyarenitrogen-richporous polymersconstructedusingtriazinebuildingblocks.Theyoftenlack long-rangeorder,buthaveexcellentrobustandrigidstructures,immense thermalandchemicalstability,highacid-baseresistivity,largesurfacearea, andtunableporesizesandstructures [61–64].ContrarytootherPOFs,the porouspropertiesofCTFscanbeeasilytunedbyvaryingtheCTFsynthesis conditions,suchastemperature,time,andcatalyst(zincchloride)ratio. Mostinterestingly,coordinatingfunctionalgroupsincorporatedinthe skeletonofCTFscanenableanchoringtransitionmetalcomplexesonthe robustandhigh-surface-areasolidsupportsandgeneratewell-defined porousimmobilizedmetalcomplexes.Consequently,diffusionofreactants, solvent(s),andproductmolecules,whichplaysakeyroleinheterogeneous catalysis,wouldbefacileandcouldleadtotheactivitiessimilartoorbetter thanhomogeneouscomplexes.Inaddition,thenumerouscoordinatingsites availableintheskeletonofCTFsallowtheimmobilizationofalargenumber ofmolecularcomplexesonthesupport,i.e.,numberofactivesitepergram ofthesupportcanbehigher,whichisalsoimportantfromanindustrial viewpoint [65–69].Finally,theundesirableinteractionscausedbytheuse oflinkersinconventionalimmobilizationmethodcanbeprevented.Hence, CTF-basedheterogenizedcomplexescanofferbothenhancedactivityand stability.
Fig.1 (A)BasicstructureofCTF;(B)IdealporenetworksofCTF;(C)Salientfeatures ofCTF.
Theformationofcross-linkedtriazine-basedpolymerviatransition metal-catalyzedtrimerizationofdinitrileswasfirstreportedin1973 [70]. However,thismaterialgainedsignificantscientificattentionin2008by Kuhn,Antonietti,andThomas,whowereinterestedinthesynthesisof microporousorganicpolymerswithintrinsicporosityandtailor-madefunctionalities [61,62].TheseresearchersdiscoveredCTFsasnewclassofhigh performancepolymerframeworkswithregularandirregularporosity. Avarietyofaromaticdinitrilecompoundsweretrimerizedintheirreport usingZnCl2 athightemperatures,particularlyabovethemoltentemperatureofZnCl2 [61–65].InspiredbytheexcellentcharactersandperformancesofCTFs,severalmethodshavebeendevelopedforthe preparationofCTFs;however,thepropertiesofthefinalproductshave beenstronglyinfluencedbythesyntheticprocess.
Todate,CTFscanbepreparedthrough:(1)ionothermaltrimerizationof carbonitrilegroupsattemperaturesrangingfrom300to600°CusingZnCl2 asacatalystandsaltmelt [61–68];(2)theSchiffbasereactionbetweenmelaminewithdifferentaldehydes [71–77];(3)nucleophilicsubstitutionofcyanuricchloridewithdifferentnucleophiles [78–83];(4)theSonogashira couplingbetweensubstitutedbromoderivativesoftriazineringswithvariousderivativesofterminalalkynes [84];(5)theYamamotoself-coupling reactionofsubstitutedbromoderivativesoftriazinerings [85,86];and(6) theFriedel-Craftsreactionbetweencyanuricchloridewithavarietyof electron-richaromaticcompounds [87–89].Therecentreviewspublished independentlybyPuthiyarajetal. [69] andArtz [90] providedetailedinformationonthesynthesisofCTFs.
Asstated,theneedforhighlyactive,selective,anddurablecatalyststhat withstandaharshreactionatmosphereisdrivingscientiststodevelopthermallyandchemicallystablesolidsupportmaterialsfortheheterogenization ofmolecularcomplexes.Inthisplatform,weintroducetheaspectsofCTFs usedfordevelopingwell-definedheterogenizedcatalystsforvariouscatalytictransformations.Here,welimitourdiscussiontoCTFspreparedby ionothermalsynthesisbecausetheyhavevariedcharacters,includingrobustnessandporerigidity,comparedtothosepreparedbyothermethods,and mostoftheheterogenizedcatalystsemploythissynthetic-basedCTFs.To date,threeclassesofcoordinatingligandsembeddedintotheCTFskeleton viaionothermalsynthesishavebeenemployedassolidchelatingligandsfor thepreparationofheterogenizedcatalysts:Pyridine,Acetylacetone,and N-heterocycliccarbenes.Therefore,wesegmentedthischapteraccording tothecoordinatingligandsincorporatedwithinCTF.
2CTFincorporatedwithpyridinicligands ThemostwidelyemployedCTFsfortheconstructionofCTF-basedheterogenizedcatalystsarepyridinic-basedCTFs.Therearetwokindsof pyridinicligands-basedCTFsthathavebeenconstructedandusedinthe heterogenizedcatalystpreparation:(1)aCTFconstructedusing2,6dicyanopyridinemonomer(Fig.2),wherethemetalsareexpectedtocoordinateviaonepyridinicnitrogenandonetriazinicnitrogen;(2)aCTF constructedusing5,5-dicyano-2,20 -bipyridinemonomer,wherethemetals areexpectedtocoordinatevia2,20 -bipyridinicnitrogen.Althoughbothare similaratfirstglance,theircharactersincludingporosity,surfacearea,electrondensity,and/orelectron-donatingabilitiesaresupposedlydifferent. 5
Fig.2 RouteofsynthesisofCTFderivedfrom2,6-dicyanopyridinebuildingblock. (AdaptedfromA.V.Bavykina,M.G.Goesten,F.Kapteijn,M.Makkee,J.Gascon,Efficient productionofhydrogenfromformicacidusingacovalenttriazineframeworksupported molecularcatalyst,ChemSusChem8(2015)809–812,withpermissionofJohnWileyand Sons.R.Palkovits,M.Antonietti,P.Kuhn,A.Thomas,F.Sch € uth,Solidcatalystsforthe selectivelow-temperatureoxidationofmethanetomethanol,Angew.Chem.Int.Ed. 48(2009)6909–6912,withpermissionofJohnWileyandSons.)
2.1Pyridinic-CTFderivedfrom2,6-dicyanopyridine buildingblock
ThepotentialviabilityofCTFsfortheimmobilizationofmolecularcatalysts wasfirstdemonstratedbyPalkovitsetal.using2,6-dicyanopyridine-based CTFfortheoxidationofmethanetomethanol(Fig.3) [91].The2,6dicyanopyridine-basedCTFwaspreparedinmoltenZnCl2 throughastepwiseincreaseoftemperature(at400°Cfor40handthen600°Cfor40h). ThedetailsofporouspropertiesafterPtimmobilizationwerenotprovided inthatstudy.AnitrogenbindingsiteofthepyridinicunitandanitrogenbindingsiteofthetriazineunitcooperativelyenabledthecoordinationofPtvia N^Nfashion.Theresultingcomplexwasstructurallysimilartothemolecular Pt-bipyrimidinecomplexreportedbyPerianaetal.,thecommercialapplicationofwhichwasrestrictedbydifficultiesintheseparationandrecyclingof thispreciousmetalcomplex [92].TheimmobilizedPtcatalystefficientlyoxidizedmethaneintomethanolwithalmostsimilaractivityandselectivitytothe molecularcatalystat200°CinthepresenceofSO3 inconcentratedsulfuric acid.TheexactnatureandchemicalenvironmentofthePtsitespriorto andafterthecatalysiswerestudiedusingacombinationofseveralsophisticated analyticalmethodsincludingsolid-state 195PtNMRspectroscopyand aberration-correctedscanningtransmissionelectronmicroscopy(AC-STEM) [93].Althoughthecatalyticreactionwasperformedunderharshreaction
Fig.3 RepresentativestructureofPt-CTF(A)anditshomogeneouscounterpart(Periana Catalyst)(B). (ReproducedfromR.Palkovits,M.Antonietti,P.Kuhn,A.Thomas,F.Schuth, Solidcatalystsfortheselectivelow-temperatureoxidationofmethanetomethanol,Angew. Chem.Int.Ed.48(2009)6909–6912,withpermissionofJohnWileyandSons.)
conditions,theefficiencyoftheimmobilizedPtcatalystwaswell-maintained uponsuccessiveruns.ThisindicatesthattheCTF-basedcatalystisthermally andchemicallystable,andmostimportantly,thecoordinatingabilityofthe nitrogenspecieswiththemetal(Pt)cationintheCTFisremarkablystrong. Inspiredbythisinterestingapproach,Bavykinaetal.employedaCTF constructedbymixing2,6-dicyanopyridineand4,40 -biphenyldicarbonitrile (1:2ratio)buildingblocksfortheimmobilizationofIrCp* unit (Cp* ¼ 1,2,3,4,5-pentamethylcyclopentadient)viaN^Ncoordination (Fig.4A) [94],similartoPtcoordinationstrategyreportedbyPalkovits etal.Mixing4,40 -biphenyldicarbonitrilewith2,6-dicyanopyridinebuildingblockmayfacilitatethediffusionofreactantandproductmolecules. TheimmobilizedIrcomplex,IrCp*@CTF,wasemployedforthecatalyticdehydrogenationofformicacidintoCO 2/H2 underbase-freeconditions.Thecatalystproducedinitia lturnoverfrequencies(TOFs)ofup to27,000h 1 andturnovernumbers(TONs)ofupto1,060,000during continuousoperationsat80° C;thisinitialTOFwasthehighestatthetime ofpublication.TheauthorslinkedtheworkingcapabilityofIrCp * @CTF inabase-freemediumwiththeinherent basicityofthepyridinicsitespresentintheCTFmatrix.Thecatalyst wasrecycledforatleastfourruns withoutanysignificantIrleachingandchangesintheoxidationstateof theIrsites.
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