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TitaniumDioxide(TiO2)andIts Applications
ForthcomingTitles
● MetalOxides:PowderTechnologies, YarubAl-Douri(ed.),9780128175057
● PalladiumOxidesMaterialProperties,SynthesisandProcessingMethods,and Applications,AlexanderM.Samoylov,VasilyN.Popov,9780128192238
● MetalOxidesforNon-volatileMemory,PanagiotisDimitrakis,IliaValov,9780128146293
● MetalOxideNanostructuredPhosphors,H.Nagabhushana,DarukaPrasad,S.C.Sharma, 9780128118528
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● MultifunctionalPiezoelectricOxideNanostructures,Sang-JaeKim,NagamalleswaraRao Alluri,YuvasreePurusothaman,9780128193327
● TitaniumDioxide(TiO2)andItsApplications,FrancescoParrino,LeonardoPalmisano, 9780128199602
● TransparentConductiveOxides,MirelaPetrutaSuchea,PetronelaPascariu,Emmanouel Koudoumas,9780128206317
● MetalOxide-BasedNanofibersandTheirApplications,VincenzoEsposito,Debora Marani,9780128206294
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● MetalOxide-CarbonHybridMaterials,MuhammadAkram,RafaqatHussain,FaheemK Butt,9780128226940
PublishedTitles
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● CeriumOxide,SalvatoreScire,LeonardoPalmisano,9780128156612
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● GasSensorsBasedonConductingMetalOxides,NicolaeBarsan,KlausSchierbaum, 9780128112243
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● MetalOxidesinHeterogeneousCatalysis,JacquesC.Vedrine,9780128116319
● Magnetic,Ferroelectric,andMultiferroicMetalOxides,BiljanaStojanovic, 9780128111802
● IronOxideNanoparticlesforBiomedicalApplications,SophieLaurent,Morteza Mahmoudi,9780081019252
● TheFutureofSemiconductorOxidesinNext-GenerationSolarCells,MonicaLira-Cantu, 9780128111659
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● MetalOxidesinSupercapacitors,DeepakDubal,PedroGomez-Romero,9780128111697
● SolutionProcessedMetalOxideThinFilmsforElectronicApplications,ZhengCui, 9780128149300
● TransitionMetalOxideThinFilm-BasedChromogenicsandDevices,PandurangAshrit, 9780081018996
TitaniumDioxide(TiO2) andItsApplications
Editedby FrancescoParrino
DepartmentofIndustrialEngineering, UniversityofTrento,Trento,Italy
LeonardoPalmisano
“Schiavello-Grillone”PhotocatalysisGroup, DepartmentofEngineering,Universityof Palermo,Palermo,Italy
SeriesEditor
GhenadiiKorotcenkov
DepartmentofTheoreticalPhysics, MoldovaStateUniversity,Chisinau,Moldova
Elsevier
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Listofcontributorsxv
Abouttheserieseditorxix
Abouttheeditorsxxi
Prefacetotheseriesxxiii
Prefacetothevolumexxvii
Section1Titaniumdioxide:synthesisand characterization1
1Introduction3
FrancescoParrinoandLeonardoPalmisano
1.1Economicaspects3 1.2Summaryofthebook6 References11
2Propertiesoftitaniumdioxide13
FrancescoParrino,FrancescaRitaPomilla,GiovanniCamera-Roda, VittorioLoddoandLeonardoPalmisano
2.1Introduction13
2.2Structuralproperties14
2.2.1StructuresofTiO2 14
2.2.2MaintechniquesusedforTiO2 structuralanalysis16 2.3Structureanddefects18
2.3.1Defectivity19
2.3.2Surfacedefectivity22
2.3.3Surfaceandlatticedistortion26
2.4TiO2 morphologies26
2.5Thermodynamicproperties29
2.6Electronicproperties32
2.7Electricalproperties33
2.8Opticalproperties35
2.9Photon-inducedbehavior39
2.10Mechanicalandrheologicalproperties42
2.10.1Mechanicalproperties42
2.10.2Rheologicalproperties46 References46
3StructuralandelectronicpropertiesofTiO2 fromfirstprinciples calculations67
SergioTosoni,GiovanniDiLibertoandGianfrancoPacchioni 3.1Introduction67
3.2ElectronicstructurecalculationsonTiO2:methodologicalaspects68
3.2.1Thebandgapissue68
3.2.2Excesselectrons(andholes)inTiO2:thelocalization problem70
3.2.3Oxygenvacancies72
3.2.4InterstitialTispecies74
3.2.5Photoexcitedcarriers75
3.3Titaniaheterojunctionsandnanoparticles:computational modelingofcutting-edgematerials76
3.3.1Separationofphotoexcitedchargecarriersintitania nanocomposites76
3.3.2Computationalmodelingoftitaniananoparticles78
3.4Conclusions81 Acknowledgments81 References81
4Synthesisandcharacterizationoftitaniumdioxideandtitanium dioxide basedmaterials87
MariannaBellardita,SedatYurdakalandLeonardoPalmisano 4.1Introduction87
4.2Preparationmethods88
4.2.1PreparationmethodsofpowderedTiO2-basedmaterials88
4.2.2PreparationmethodsofTiO2 film104
4.3CharacterizationtechniquesofTiO2 109
4.3.1X-raydiffraction109
4.3.2Scanningelectronmicroscopy115
4.3.3Transmissionelectronmicroscopy121
4.3.4Brunauer Emmett Teller-specificsurfacearea determination127
4.3.5Diffusereflectancespectroscopy135
4.3.6Photoluminescencespectroscopy141
4.3.7X-rayphotoelectronspectroscopy144
4.3.8Thermalgravimetricanalysis147 References152
Section2Energyapplications167
5Synthetic,naturalandbioinspireddyesasTiO2 sensitizers insustainablesolarcells169
NunzioGenitoriandGaetanoDiMarco 5.1Introduction169
5.1.1Photovoltaictechnology169
5.1.2Dye-sensitizedsolarcells171
5.2Semiconductors176
5.2.1Bandsformation176
5.2.2Theoccupationoftheorbitals176
5.2.3Titaniumdioxide177
5.3Dyes180
5.3.1Syntheticdyes180
5.3.2Naturaldyes182
5.3.3Computationaldetails189
5.3.4Bioinspired191
5.4Otherfunctionalmaterials191
5.4.1CharacteristicsandperformanceofCEs191
5.4.2Characteristicsandperformanceofelectrolytes192
5.5AssemblyandcharacterizationsforDSSCs193
5.5.1Developmentofphotoanodesandcathodes193
5.5.2Spectroscopictechniques193
5.5.3Cyclicvoltammetry194
5.5.4Roughnessanddesorptionfactor196
5.5.5CharacteristicI-Vcurves197
5.5.6Quantumefficiency:IPCE,APCE,andLHE201
5.5.7Electrochemicalimpedancespectroscopy203
5.5.8Tafelelectroanalysis204
5.6Conclusions206 References207
6TiO2-basedmaterialsforphotocatalytichydrogenproduction211 MariaVittoriaDozziandElenaSelli
6.1Introduction211
6.2PhotocatalyticwatersplittingwithTiO2 212
6.3DevelopmentofsensitiveTiO2-basedphotocatalystsforH2 generation214
6.3.1Bandgapengineering214
6.3.2SurfaceTiO2 sensitization217
6.4SeparationofphotogeneratedchargesinTiO2-based photocatalystsforH2 generation218
6.4.1ChargeseparationinTiO2 phasejunctions218
6.4.2Chargeseparationinshape-controlledanataseTiO2 218
6.4.3NoblemetalnanoparticlesdepositionandSchottky junctionfabrication220
6.4.4Fabricationofheterojunctions222
6.4.5LoadingcocatalystsonTiO2 225
6.5Sacrificialagentsinphotocatalytichydrogenproduction: fromoverallwatersplittingtobiomassreforming228
6.6Conclusionandperspectives230 References230
7TiO2-baseddevicesforenergy-relatedapplications241
C.G.JothiPrakashandR.Prasanth
7.1Introduction241
7.1.1Titaniumdioxideforenergyharvesting242
7.1.2Titaniumdioxideforenergystorage242
7.2Energystorageapplications243
7.2.1Supercapacitors243
7.2.2Batteries250
7.2.3Hydrogenproductionandstorage254
7.2.4Others258
7.3Conclusionandoutlook260 References260
8HeattransferbyusingTiO2 nanofluids267
VittorioLoddoandGiovanniCameraRoda
Listofabbreviations267
8.1Introduction267
8.2PreparationandcharacterizationofTiO2 nanofluids270
8.2.1Nanoparticlespreparation270
8.2.2Preparationofnanofluids272
8.2.3Parametersinfluencingtheaggregationandstability ofTiO2 nanofluids274
8.2.4Nanoparticlesizemeasurements274
8.2.5Z-potentialmeasurements275
8.2.6pHmeasurements275
8.3HeatconductioninTiO2 nanofluids276
8.3.1Influenceofparticleload278
8.3.2Influenceoftemperature278
8.3.3Influenceofthermalconductivityofthebasefluid279
8.3.4Influenceofparticleclustersizeandshapeonthermal conductivity279
8.3.5Influenceofsurfactant285
8.3.6Influenceofultrasonictreatment285
8.4HeatconvectioninTiO2 nanofluids285
8.4.1Forcedconvection287
8.4.2Naturalconvection293
8.5BoilingheattransferofTiO2 nanofluids295
8.5.1Influenceofnanoparticletype296
8.5.2Influenceofparticleloading296
8.5.3Influenceofsurfaceroughness297
8.5.4Influenceoftheheatermaterial298
8.5.5Influenceofionicadditive298
8.6ApplicationsofTiO2 nanofluids298
8.7Futureinvestigations299 References300
Section3TiO2 inourlife309
9TiO2 aswhitepigmentandvalorizationofthewastecoming fromitsproduction311 ManuelJesu´sGa´zquez,SilviaMarı´aPe´rezMoreno andJuanPedroBolı´var
9.1Introduction311
9.1.1Titaniumminerals312
9.1.2Titaniumorepurification313
9.2Routesforthemanufactureoftitaniumdioxide pigments(PigmentWhite6)315
9.2.1Thechlorideprocess315
9.2.2Sulfateprocess317
9.3PropertiesandapplicationsofPigmentWhite6319
9.3.1Properties319
9.3.2Applications321
9.4Valorizationofcoproductsandwastesgenerated327
9.4.1Mainwastesgeneratedinthesulfateprocess328
9.4.2Mainwastesgeneratedinthechlorideprocess329 References330
10Titaniumdioxide basednanomaterials:applicationoftheir smartpropertiesinbiomedicine337 GiadaGrazianaGenchi
10.1Introduction337
10.2Smartpropertiesoftitaniumdioxide basednanomaterials338
10.2.1Advancedphotodynamictherapyapproachedbased onhybridtitaniumdioxide basednanomaterials339
10.2.2Advancedsonodynamictherapyapproachedbased onhybridtitaniumdioxide basednanomaterials342
10.3Tissueengineering343
10.4Drugdelivery345
10.5Otherapplications349
10.6Conclusionandperspectives350 References351
11TiO2 inthefoodindustryandcosmetics353 AnnachiaraBerardinelliandFilippoParisi
11.1Introduction353
11.2Titaniumdioxideasfoodadditive354
11.2.1Titaniumdioxideinfood354
11.2.2Influenceoftitaniumdioxideonhumanhealth355
11.3Titaniumdioxideforfoodpreservation357
11.3.1Antibacterialeffects357
11.3.2Ethylenedegradation360
11.3.3Activepackaging361
Contents
11.4Titaniumdioxideincosmeticsandpersonalcareproducts362
11.4.1Regulations364
11.4.2Safetyofsunscreens364 11.5Conclusion365 References366
12Titaniumdioxide:antimicrobialsurfacesandtoxicityassessment373 ValeriaDeMatteis,MariafrancescaCascioneandRosariaRinaldi 12.1Introduction373
12.2Antibacterialandantimicoticproperties375
12.2.1AdverseeffectofTiO2 onbacteria375
12.2.2AdverseeffectsofTiO2 onfungi378
12.3ToxicityassessmentonTiO2 NPs378
12.3.1Regulations378
12.3.2Exposurerouteandbiodistrubution379
12.4Antimicrobialsurfaces383 12.5Conclusion386 Conflictsofinterest386 Acknowledgments386 References386
13FunctionalizationofglassbyTiO2-basedself-cleaningcoatings395 CorradoGarlisi,GabrieleScandura,AhmedYusuf andSamarAlJitan
13.1Introduction395
13.2Mainprinciplebehindself-cleaningbehavior396
13.3Applicationsofself-cleaningglassandmain commercialproducts402
13.3.1Commercialself-cleaningglasses405
13.4DopedTiO2 basedcoatingsforimprovedself-cleaningability408
13.4.1Mechanismofdoped-TiO2 coatingsforglass408
13.4.2Synthesisstrategies412
13.5Futuretendencies:multilayercoatingsformultifunctionalglass414
13.5.1Multilayerstructuresforimprovedself-cleaningand antireflectiveability414
13.5.2Self-cleaningandenergy-savingmultilayerstructures417 13.6Conclusion420 References421
14TiO2 asasourceoftitanium429
XingliZou,ZhongyaPang,LiJiandXionggangLu
14.1TiO2 productionfromtitaniumminerals429
14.1.1Productionoftitanium-richslagfromtitaniumminerals429
14.1.2ProductionofTiO2 fromtitanium-richslag431
14.2TheKrollprocessfromTiO2 toTi433
14.3ElectrolyticproductionofTifromTiO2 inhigh-temperature moltensalts438
14.4ElectrodepositionofTiinlow-temperatureliquidsalts445 Acknowledgments446 References447
15TiO2 inthebuildingsector449 ElisaFranzoni,MariaChiaraBignozziandElisaRambaldi 15.1Introduction449
15.2TiO2 incement-basedmaterials449
15.2.1GeneralgoalsoftheuseofTiO2 in cement-basedmaterials449
15.2.2UseofTiO2 forfunctionalcement-basedmaterials451
15.2.3UseofTiO2 forstructuralcement-basedmaterials458
15.2.4Patentsoncement-basedmaterialswithTiO2 461
15.3TiO2 ingeopolymers461
15.4TiO2 inceramictiles462
15.4.1Ceramictilesproduction462
15.4.2ExploitationofTiO2 inceramictiles464
15.4.3Internationalpatentsonphotocatalyticceramictiles467
15.4.4Standards468
15.5TiO2 inculturalheritageconservation468
15.6EnvironmentalandhealthconcernsintheuseofTiO2 in buildingmaterials470
15.7Conclusionandperspectives473 References474
Section4TiO2 devicesandtheirapplications481
16TiO2 oxidesforchromogenicdevicesanddielectricmirrors483 AlessandroCannavaleandGiovanniLerario
16.1TiO2 inelectrochromicdevices483
16.1.1Depositiontechniques484
16.2TiO2 inphoto-electrochromicdevices488
16.3TiO2 opticalproperties492
16.4ModelingdistributedBraggreflectors493
16.5Blochsurfacewavesandmicrocavitymodes498
16.6Conclusion501 References501
17TiO2 inmemristorsandresistiverandomaccessmemorydevices507 AndreaZaffora,FrancescoDiFranco,RobertoMacaluso andMonicaSantamaria
17.1Introduction507
17.2Fundamentalsonresistiveswitching508
17.2.1Electrochemicalmetallizationmemories508
17.2.2Valencechangememories510
17.3TiO2 inmemristorsandresistiverandomaccessmemories: fabricationmethodsandperformances512
17.3.1Anodizing512
17.3.2Atomiclayerdeposition516
17.3.3Sputtering519
17.4Conclusionsandperspectives521 References522
18ApplicationsofTiO2 insensordevices527
GiuseppeMele,RobertaDelSoleandXiangfeiLu¨
Listofabbreviations527
18.1Introduction528
18.2Titaniumdioxideinsensorfield:principlesandmechanisms ofaction530
18.2.1Mechanismofsensing531
18.3Gassensors534
18.3.1H2O(humidity)536
18.3.2Dihydrogen(H2)538
18.3.3Dioxygen(O2)539
18.3.4CO2
18.3.5NH3
18.3.6CO543
18.3.7NO2 544
18.3.8Volatileorganiccompounds545 18.4Biosensors552
18.4.1Glucose554
18.4.2DNAandbiomarkers555
18.4.3Pesticides556
18.4.4Cholesterolderivatives558
18.4.5H2O2 558
18.4.6Urea559
18.4.7Glutamate560
18.4.8Bacteria(Escherichiacoli,etc.)560
18.4.9Otheranalytes561
18.5Sensorsforenvironmentalapplications562
18.5.1Detectionoforganicpollutants563
18.5.2Detectionofdyes565
18.5.3TiO2 inmolecularimprintingtechnology567
18.5.4Metalionsdetection568
18.6Fabricationofnanoscalesensorsandfutureprospects569 18.7Conclusion571 References572
19TiO2 photocatalysisforenvironmentalpurposes583 OlgaSacco,VincenzoVaianoandDianaSannino
19.1Generaloverviewonairandwaterpollution583
19.2Generalremarksonadvancedoxidationprocesses586
19.3TiO2 photocatalysisfortheremovalofvolatileorganic compoundsfromgaseousstream589
19.4TiO2 photocatalysisforindoorairpurification591
19.4.1TiO2 photocatalysiswithforcedair592
19.4.2TiO2 photocatalysisinindoorenvironments596
19.5TiO2 photocatalysisfortheremovaloforganicpollutants fromwaterandwastewater600
19.6Conclusionandfutureperspectives602 References603
20FinechemistrybyTiO2 heterogeneousphotocatalysis609 GiuseppeMarcı`,ElisaI.Garcı´a-Lo´pezandLeonardoPalmisano
20.1Introduction609
20.2Reactionsofpartialoxidation610
20.2.1Oxidationofalcoholstoaldehydes610
20.2.2Hydroxylationofaromaticcompounds612
20.2.3Epoxidationofalkenes614
20.3Reactionsofpartialreduction615
20.3.1Hydrogenationofdoubleandtriple carbon carbonbonds615
20.3.2Reductionofcarbonyls617
20.3.3Reductionof N-containingfunctionalgroups619
20.4Reactionsofalkylation626
20.4.1Reactionsofaddition626
20.4.2Substitutionreactionsinaromaticcompounds627
20.4.3Reactionsofcarbonylalkylation629
20.5Conclusion631 References631
21CatalyticapplicationsofTiO2
637 SalvatoreScire`,RobertoFiorenza,MariannaBellardita andLeonardoPalmisano
21.1Introduction637
21.2Titaniaascatalyticsupport:roleofthestrong metal supportinteraction638
21.3Theroleofdefectsoncatalyticperformances640
21.4Mainreactionsinvolvingtitania-basedcatalyst641
21.4.1NOx removal641
21.4.2Deaconprocess644
21.4.3Reactionswithsulfur-richcompounds646
21.4.4Directsynthesisofhydrogenperoxide649
21.4.5Fischer Tropschsynthesis651
21.4.6Water gasshiftreaction653
21.4.7CO2 methanation655
21.4.8Biofuelsproduction656
21.4.9Dehydrogenations,selectiveoxidations,and hydrogenations658
21.5Conclusionandoutlooks666 References667
Listofcontributors
SamarAlJitan DepartmentofChemicalEngineering,KhalifaUniversity,Abu Dhabi,UnitedArabEmirates;ResearchandInnovationCenteronCO2 andH2 (RICHCenter),KhalifaUniversity,AbuDhabi,UnitedArabEmirates
MariannaBellardita DepartmentofEngineering,UniversityofPalermo,Palermo, Italy
AnnachiaraBerardinelli DepartmentofIndustrialEngineering,Universityof Trento,Trento,Italy;CenterAgricultureFoodEnvironment,UniversityofTrento, Trento,Italy
MariaChiaraBignozzi DepartmentofCivil,Chemical,Environmentaland MaterialsEngineering,AlmaMaterStudiorum UniversityofBologna,Bologna, Italy
JuanPedroBolı´var DepartmentofIntegratedSciences,FacultyofExperimental Sciences,UniversityofHuelva,Huelva,Spain;ResearchCentreofNatural Resources,HealthandtheEnvironment(RENSMA),UniversityofHuelva,Huelva, Spain
GiovanniCamera-Roda DepartmentofCivil,Chemical,Environmental,and MaterialsEngineering,UniversityofBologna,Bologna,Italy
AlessandroCannavale DepartmentofSciencesinCivilEngineeringand Architecture,PolytechnicUniversityofBari,Bari,Italy
MariafrancescaCascione DepartmentofMathematicsandPhysics“EnnioDe Giorgi”,UniversityofSalento,Lecce,Italy
ValeriaDeMatteis DepartmentofMathematicsandPhysics“EnnioDeGiorgi”, UniversityofSalento,Lecce,Italy
RobertaDelSole DepartmentofEngineeringforInnovation,Universityof Salento,Lecce,Italy
FrancescoDiFranco DepartmentofEngineering,UniversityofPalermo, Palermo,Italy
GiovanniDiLiberto DepartmentofMaterialsScience,UniversityofMilanoBicocca,Milan,Italy
GaetanoDiMarco InstituteforChemicalandPhysicalProcesses(IPCF),National ResearchCouncil,Messina,Italy
MariaVittoriaDozzi DepartmentofChemistry,UniversityofMilan,Milan,Italy
RobertoFiorenza DepartmentofChemicalSciences,UniversityofCatania, Catania,Italy
ElisaFranzoni DepartmentofCivil,Chemical,EnvironmentalandMaterials Engineering,AlmaMaterStudiorum UniversityofBologna,Bologna,Italy
ElisaI.Garcı´a-Lo ´ pez DepartmentofBiological,ChemicalandPharmaceutical SciencesandTechnologies(STEBICEF),UniversityofPalermo,Palermo,Italy
CorradoGarlisi DepartmentofChemicalEngineering,KhalifaUniversity,Abu Dhabi,UnitedArabEmirates;ResearchandInnovationCenteronCO2 andH2 (RICHCenter),KhalifaUniversity,AbuDhabi,UnitedArabEmirates
ManuelJesu ´ sGa ´ zquez DepartmentofAppliedPhysics,MarineResearchInstitute (INMAR),UniversityofCadiz,Ca ´ diz,Spain
GiadaGrazianaGenchi SmartBio-Interfaces,IstitutoItalianodiTecnologia, Pontedera,Italy
NunzioGenitori InstituteforChemicalandPhysicalProcesses(IPCF),National ResearchCouncil,Messina,Italy
LiJi StateKeyLaboratoryofASICandSystem,SchoolofMicroelectronics, FudanUniversity,Shanghai,P.R.China
C.G.JothiPrakash MadanjeetSchoolofGreenEnergyTechnology,Pondicherry CentralUniversity,Pondicherry,India
GiovanniLerario CNRNanotec,InstituteofNanotechnology,Lecce,Italy
VittorioLoddo DepartmentofEngineering,UniversityofPalermo,Palermo,Italy
XiangfeiLu ¨ SchoolofWaterandEnvironment,Chang’AnUniversity,Xi’an, P.R.China
XionggangLu StateKeyLaboratoryofAdvancedSpecialSteel,Schoolof MaterialsScienceandEngineering,ShanghaiUniversity,Shanghai,P.R.China
RobertoMacaluso DepartmentofEngineering,UniversityofPalermo,Palermo, Italy
GiuseppeMarcı ` “Schiavello-Grillone”PhotocatalysisGroup,Departmentof Engineering(DI),UniversityofPalermo,Palermo,Italy
GiuseppeMele DepartmentofEngineeringforInnovation,UniversityofSalento, Lecce,Italy
SilviaMarı´aPe ´ rezMoreno DepartmentofIntegratedSciences,Facultyof ExperimentalSciences,UniversityofHuelva,Huelva,Spain;ResearchCentreof NaturalResources,HealthandtheEnvironment(RENSMA),UniversityofHuelva, Huelva,Spain
GianfrancoPacchioni DepartmentofMaterialsScience,UniversityofMilanoBicocca,Milan,Italy
LeonardoPalmisano “Schiavello-Grillone”PhotocatalysisGroup,Departmentof Engineering(DI),UniversityofPalermo,Palermo,Italy;Departmentof Engineering,UniversityofPalermo,Palermo,Italy
ZhongyaPang StateKeyLaboratoryofAdvancedSpecialSteel,Schoolof MaterialsScienceandEngineering,ShanghaiUniversity,Shanghai,P.R.China
FilippoParisi DepartmentofPhysicsandChemistry,UniversityofPalermo, Palermo,Italy
FrancescoParrino DepartmentofIndustrialEngineering,UniversityofTrento, Trento,Italy
FrancescaRitaPomilla DepartmentofMaterialsScience,UniversityofMilanoBicocca,Milano,Italy
R.Prasanth MadanjeetSchoolofGreenEnergyTechnology,PondicherryCentral University,Pondicherry,India
ElisaRambaldi CentroCeramico,Bologna,Italy
RosariaRinaldi DepartmentofMathematicsandPhysics“EnnioDeGiorgi”, UniversityofSalento,Lecce,Italy
OlgaSacco DepartmentofChemistryandBiology“A.Zambelli”,Universityof Salerno,Fisciano,Italy
DianaSannino DepartmentofIndustrialEngineering,UniversityofSalerno, Fisciano,Italy
MonicaSantamaria DepartmentofEngineering,UniversityofPalermo,Palermo, Italy
GabrieleScandura DepartmentofChemicalEngineering,KhalifaUniversity,Abu Dhabi,UnitedArabEmirates;ResearchandInnovationCenteronCO2 andH2 (RICHCenter),KhalifaUniversity,AbuDhabi,UnitedArabEmirates
SalvatoreScire ` DepartmentofChemicalSciences,UniversityofCatania,Catania, Italy
ElenaSelli DepartmentofChemistry,UniversityofMilan,Milan,Italy
SergioTosoni DepartmentofMaterialsScience,UniversityofMilano-Bicocca, Milan,Italy
VincenzoVaiano DepartmentofIndustrialEngineering,UniversityofSalerno, Fisciano,Italy
SedatYurdakal DepartmentofChemistry,UniversityofAfyonKocatepe, Afyonkarahisar,Turkey
AhmedYusuf DepartmentofChemicalEngineering,KhalifaUniversity,Abu Dhabi,UnitedArabEmirates;ResearchandInnovationCenteronCO2 andH2 (RICHCenter),KhalifaUniversity,AbuDhabi,UnitedArabEmirates
AndreaZaffora DepartmentofEngineering,UniversityofPalermo,Palermo,Italy
XingliZou StateKeyLaboratoryofAdvancedSpecialSteel,SchoolofMaterials ScienceandEngineering,ShanghaiUniversity,Shanghai,P.R.China
Abouttheserieseditor
GhenadiiKorotcenkov earnedhisPhDinmaterial sciencesin1976andhisdoctorofsciencedegree(doctor habilitate)inphysicsin1990.Hehasmorethan45years ofexperienceasascientificresearcher.Foralongtime, hehasbeentheleaderofthegassensorgroupandmanager ofvariousnationalandinternationalscientificandengineeringprojectscarriedoutintheLaboratoryofMicroandOptoelectronics,TechnicalUniversityofMoldovaand supportedfrominternationalfoundationsandprograms suchastheCRDF,theMRDA,theICTP,theINTAS,the INCO-COPERNICUS,theCOST,andtheNATO.From 2007to2008,hewasaninvitedscientistintheKoreanInstituteofEnergy Research,Daejeon,SouthKorea.Then,untiltheendof2017,hewasaresearch professorattheSchoolofMaterialsScienceandEngineeringattheGwangju InstituteofScienceandTechnology,Gwangju,SouthKorea.Currently,heisthe chiefscientificresearcher(researchprofessor)attheDepartmentofPhysicsand EngineeringattheMoldovaStateUniversity,Chisinau,theRepublicofMoldova.
Dr.G.Korotcenkoviseithertheauthororeditorof39books,includingthe11volume ChemicalSensors seriespublishedbytheMomentumPress(UnitedStates), 15-volume ChemicalSensors seriespublishedbyHarbinInstituteofTechnology Press(China),3-volume PorousSilicon: FromFormationtoApplication published byCRCPress(UnitedStates),2-volume HandbookofGasSensorMaterials publishedbySpringer(UnitedStates),and3-volume HandbookofHumidity Measurements publishedbyCRCPress(UnitedStates).Inaddition,atpresent,he isaseries’editorof MetalOxides series,whichisbeingpublishedbyElsevier. Startingfrom2017,already18volumeshavebeenpublishedwithintheframework ofthatseries.
Dr.G.Korotcenkovistheauthorandcoauthorofmorethan650scientificpublications,including30reviewpapers,38bookchapters,andmorethan200articles publishedinpeer-reviewedscientificjournals[h-factor 5 42(Scopus)andhfactor 5 53(GoogleScholarcitation)].Inthemajorityofpublications,heisthefirst author.Besides,heistheholderof18patentsandhaspresentedmorethan250 reportsatnationalandinternationalconferences,including17invitedtalks.Hewas acoorganizerofmorethan20internationalscientificconferences.
ResearchactivitiesofDr.G.KorotcenkovarehonoredbytheHonoraryDiploma oftheGovernmentoftheRepublicofMoldova(2020),thePrizeoftheAcademy ofSciencesofMoldova(2019),anawardoftheSupremeCouncilofScienceand
AdvancedTechnologyoftheRepublicofMoldova(2004);PrizeofthePresidents oftheUkrainian,Belarus,andMoldovanAcademiesofSciences(2003);and NationalYouthPrizeoftheRepublicofMoldovainthefieldofscienceandtechnology(1980),amongothers.HealsoreceivedafellowshipfromtheInternational ResearchExchangeBoard(IREX,UnitedStates,1998),BrainKorea21Program (2008 12),andBrainpoolProgram(Korea,2007 08and2015 17).
Abouttheeditors
FrancescoParrino isanAssistantProfessorofChemistryattheUniversityofTrento, Italy.HegraduatedcumlaudeinChemicalEngineeringfromtheUniversityof Palermoin2005andgotaPhDinInorganicChemistryfromtheFriedrich Alexander UniversityofErlangen Nu ¨ rnberg,Germany,in2009.Hisresearchactivitydealswith thepreparationandcharacterizationofphotocatalystsfordegradationofpollutants andforgreensynthesisoforganicmolecules.Hisscientificproductionconjugates mechanisticandfundamentalaspectsofheterogeneousphotocatalysiswithengineeringissuesforindustrialapplications.Hehasauthoredapproximately80jointpapersin collaborationwithscientistsfromallovertheworldandseveralcommunicationsfor internationalconferencesonthesetopics.
LeonardoPalmisano isaProfessorofChemistryattheDepartmentofEngineering oftheUniversityofPalermo,Italy.Hisresearchhasfocusedonthefieldofheterogeneousphotocatalysisandvarioustopicsconcerningpreparation,characterizationwith manybulkandsurfacetechniques,andtestingofvarioustypesofphotocatalysts.He hascoordinatedmanynationalandinternationalresearchprojects(bilateralprojects withSpain,India,andEgypt)andhasobtainedfinancialsupportbytheEuropean UniontocarryoutexperimentswiththesolarphotoreactorsatPlataformaSolarde Almerı´a(Spain).Hehascollaboratedwithmanyscientistsfromallovertheworldto publishmorethan300jointpapersininternationaljournals,books,andconference proceedings.Healsoholdsfivepatents.
Prefacetotheseries
Thefieldofsynthesis,study,andapplicationofmetaloxidesisoneofthemostrapidlyprogressingareasofscienceandtechnology.Metaloxidesareoneofthemost ubiquitouscompoundgroupsonearth,whichhaslargevarietyofchemicalcompositions,atomicstructures,andcrystallineshapes.Inaddition,metaloxidesare knowntopossessuniquefunctionalitiesthatareeitherabsentorinsignificantly presentinothersolidmaterials.Inparticular,metaloxidesrepresentanassorted andappealingclassofmaterials,propertiesofwhichexhibitafullspectrumofelectronicproperties—frominsulatingtosemiconducting,metallic,andsuperconducting.Moreover,almostalltheknowneffects,includingsuperconductivity, thermoelectriceffects,photoelectricaleffects,luminescence,andmagnetism,canbe observedinmetaloxides.Thereforemetaloxideshaveemergedasanimportant classofmultifunctionalmaterialswitharichcollectionofproperties,whichhave greatpotentialfornumerousdeviceapplications.Specificpropertiesofthemetal oxides—suchasthewidevarietyofmaterialswithdifferentelectrophysical,optical, andchemicalcharacteristics;theirhighthermalandtemporalstability;andtheir abilitytofunctioninharshenvironments—makemetaloxidesverysuitablefor designingtransparentelectrodes,high-mobilitytransistors,gassensors,actuators, acousticaltransducers,photovoltaicandphotonicdevices,photo-andheterogeneous catalysts,solid-statecoolers,high-frequencyandmicromechanicaldevices,energy harvestingandstoragedevices,nonvolatilememories,andmanyothersintheelectronics,energy,andhealthsectors.Inthesedevices,metaloxidescanbesuccessfullyusedassensingoractivelayers,substrates,electrodes,promoters,structure modifiers,membranes,andfibers,thatis,thesecanbeusedasbothactiveandpassivecomponents.
Amongotheradvantagesofmetaloxidesarethelowfabricationcostandrobustnessinpracticalapplications.Furthermore,themetaloxidescanbepreparedinvariousformssuchasceramics,thickfilms,andthinfilm.Atthatforthinfilm depositioncanbeuseddepositiontechniquesthatarecompatiblewithstandard microelectronictechnology.Thelastfactorisveryimportantforlarge-scaleproduction,becausethemicroelectronicapproachpromoteslowcostformassproduction, offersthepossibilityofmanufacturingdevicesonachip,andguaranteesgood reproducibility.Variousmetaloxidesnanostructures,includingnanowires,nanotubes,nanofibers,core-shellstructures,andhollownanostructures,canalsobesynthesized.Asitisknown,thefieldofmetaloxide–nanostructuredmorphologies (e.g.,nanowires,nanorods,andnanotubes)hasbecomeoneofthemostactive researchareaswithinthenanosciencecommunity.
Theabilitytocreateavarietyofmetaloxide basedcompositesandtosynthesizevariousmulticomponentcompoundssignificantlyexpandtherangeofpropertiesthatmetaloxide basedmaterialscanhave,makingtheseatrulyversatile multifunctionalmaterialforwidespreaduse.Asitisknown,smallchangesintheir chemicalcompositionandatomicstructurecanbeaccompaniedbythespectacular variationinpropertiesandbehaviorofmetaloxides.Evennow,advancesinsynthesizingandcharacterizingtechniquesarerevealingnumerousnewfunctionsofmetal oxides.
Takingintoaccounttheimportanceofmetaloxidesforprogressinmicroelectronics,optoelectronics,photonics,energyconversion,sensor,andcatalysis,various booksdevotedtothisclassofmaterialshavebeenpublished.However,oneshould notethatsomebooksfromthislistaretoogeneral,somearecollectionsofvarious originalworkswithoutanygeneralizations,andotherswerepublishedmanyyears ago.But,duringpastdecades,greatprogresshasbeenmadeonthesynthesisas wellasthestructural,physical,andchemicalcharacterizationandapplicationof metaloxidesinvariousdevices,andalargenumberofpapershavebeenpublished onmetaloxides.Inaddition,tillnow,manyimportanttopicsrelatedtometaloxides studyandapplicationhavenotbeendiscussed.Toremedythesituationinthisarea, wedecidedtogeneralizeandsystematizetheresultsofresearchinthisdirection andtopublishaseriesofbooksdevotedtometaloxides.
Oneshouldnotethattheproposedbookseries MetalOxides isthefirstone, devotedonlytometaloxides.Webelievethatcombiningbooksonmetaloxidesin aseriescouldhelpreadersinsearchingrequiredinformationonthesubject.Inparticular,weplanthatthebooksfromourseries,whichhaveaclearspecializationby itscontent,willprovideinterdisciplinarydiscussionforvariousoxidematerials withawiderangeoftopics,frommaterialsynthesisanddepositiontocharacterizations,processing,andthentodevicefabricationsandapplications.Thisbookseries ispreparedbyateamofhighlyqualifiedexperts,whichguaranteesitshighquality.
Ihopethatourbookswillbeusefulandcomfortableinuse.Iwouldalsoliketo hopethatreaderswillconsiderthis MetalOxides bookserieslikeanencyclopedia ofmetaloxideswhichenablestounderstandtheirpresentstatus,toestimatethe roleofmultifunctionalmetaloxidesindesignofadvanceddevices,andthenbased onobservedknowledgetoformulatenewgoalsforfurtherresearch.
Theintendedaudienceofpresentbookseriesisscientistsandresearchers,workingorplanningtoworkinthefieldofmaterialsrelatedtometaloxides,thatis, scientistsandresearcherswhoseactivitiesarerelatedtoelectronics,optoelectronics, energy,catalysis,sensors,electricalengineering,ceramics,biomedicaldesigns,etc. Ibelievethatthis MetalOxides bookserieswillalsobeinterestingforpracticing engineersorprojectmanagersinindustriesandnationallaboratories,whichwould liketodesignmetaloxide baseddevices,butdonotknowhowtodoitandhowto selectoptimalmetaloxideforspecificapplications.Withmanyreferencestothe vastresourceofrecentlypublishedliteratureonthesubject,thisbookserieswillbe servingasasignificantandinsightfulsourceofvaluableinformation,providing scientistsandengineerswithnewinsightsforunderstandingandimprovingexisting
metaloxide baseddevicesandfordesigningnewmetaloxide basedmaterials withnewandunexpectedproperties.
Ialsobelievethatthis MetalOxides bookserieswouldbeveryhelpfulforuniversitystudents,postdocs,andprofessors.Thestructureofthesebooksoffersa basisforcoursesinthefieldofmaterialsciences,chemicalengineering,electronics, electricalengineering,optoelectronics,energytechnologies,environmentalcontrol, andmanyothers.Graduatestudentscouldalsofindthebookseriestobeveryuseful intheirresearchandunderstandingfeaturesofmetaloxidessynthesis,study,and applicationofthismultifunctionalmaterialinvariousdevices.Wearesurethatall ofthemwillfindtheinformationtobeveryusefulfortheiractivity.
Finally,Ithankallcontributingauthorsandbookeditorswhohavebeen involvedinthecreationofthesebooks.Iamthankfulthattheyagreedtoparticipate inthisprojectandfortheireffortsinthepreparationofthesebooks.Withouttheir participation,thisprojectwouldhavenotbeenpossible.Ialsoexpressmygratitude toElsevierforgivingustheopportunitytopublishthisseries.Iespeciallythankall teamsofeditorialofficeatElsevierfortheirpatienceduringthedevelopmentof thisprojectandforencouragingusduringthevariousstagesofpreparation.
GhenadiiKorotcenkov
Prefacetothevolume
Thechaptersofthisbookreportinformationontitaniumdioxidebothfromatheoreticalandapplicativepointofview.Theimportanceofthismaterialisduetoits peculiarstructural,physicochemical,andintrinsicelectronicproperties.Although concernshavebeenraisedinrecentyearsabouttheuseofTiO2 ontheskinandas anadditiveinsomefoodsoritspresenceintheenvironmentasnanoparticles,its annualproductionintheformofapowderisbetweenabout5and10milliont.In fact,thisoxidehasproventobeveryusefulinmanyapplicationsascanbeunderstoodbyreadingthisbook.Inparticular,corrosionresistance,brilliance,andelectronicpropertiesmakeitanessentialconstituentforpaints,inks,andothertypesof materialsanddevices.Itsphotocatalyticactivity,directedtowardtheoxidationof harmfulsubstancesbothinliquid solidandingas solidsystems,andmore recentlytowardselectivephotosynthesis,isintensivelystudiedwiththeaimoffindingconvenientapplicationsfromanindustrialpointofview.Thebookiscertainly notexhaustivebutattemptstogiveanoverviewascompleteaspossibleforthe readerwhomaybeinterestedinoneormorefieldsinwhichTiO2 playsanimportantrole.Wealsowanttoemphasizethattheauthorshavesetthetopicscoveredin thevariouschaptersinsuchawaythatreaderswhowishtohaveadeeperunderstandingcaneasilyfindthenecessaryliteratureamongthereferencescited.Among metaloxides,titaniumdioxideisoneofthemostversatile,andthedifferences betweenthepropertiesofthethreemostimportantpolymorphicforms,namely, anatase,brookite,andrutile,inouropinion,havenotyetbeensufficientlystudied. WebelievethatthesimultaneouspresenceofdifferentTiO2 phasesinparticular ratiosand/ortheformationofcompositesalsowithotherspeciescancontinueto giveencouragingresultsinallfieldsofapplication,aswellasbeingastimulusfor athoroughbasicstructuralandsurfaceresearch.Intheintroductorychapter,additionalinformationonthestructureofthebookwillbereported,alongwithamore detaileddescriptionoftheroleplayedbyTiO2 invariousfields.Wewishtothank alltheauthorsverymuchfortheirenthusiasticcontributioninthepreparationof thisbookwhichwehopewillbeusefultostudents,researchers,andworkers involvedinactivitieswhereTiO2 isanessentialmaterial.Finally,specialthanksgo toElsevierandtothestaffwhoaccompanieduswithgreatprofessionalisminthis challenging,yetrewardingadventure.
FrancescoParrinoandLeonardoPalmisano
Introduction FrancescoParrino1 andLeonardoPalmisano2
1DepartmentofIndustrialEngineering,UniversityofTrento,Trento,Italy, 2DepartmentofEngineering,UniversityofPalermo,Palermo,Italy
1.1Economicaspects
TheindustrialsuccessofTiO2 consistsmainlyinitsuniquepropertiesasapigment [1].Thecoveringabilityoftitaniumdioxideisevennotcomparablewiththatprovidedbypossiblealternatives.Paintformulationscontainingotherwhitepigments wouldrequirehigheramountsandmanymorelayersofpainttoachievethesame coveringeffect.Thisismainlyduetothehighrefractiveindex(RI)ofTiO2,which canreachvaluesupto2.73fortherutilephase [2].Infact,theoverallpathlength oflightthroughafilmpossessingahighRIisshorterthanthatthroughafilmwith lowerRI.ThereforethehighertheRI,thelowerthethicknessbelowwhichthefilm appearswhiteandopaque.SizeanddistributionofTiO2 particlesmustbecontrolledduringtheproductionprocess,astheyalsoaffectfinalpaintpropertiessuch asgloss,dispersion,andhiding.Forinstance,lightscatteringisoptimizedforwelldispersedTiO2 particlesofsizelessthan0.5 µm,whileglossanddispersionofthe paintarenegativelyaffectedforlargerparticles [3].
OthergreatbenefitsofferedbyTiO2 withrespecttootherwhitepigmentsareits highresistancetocorrosionandphotocorrosionanditsuniqueopticalproperties. Generally,TiO2 particlesinpaintsarecoveredwithalumina,silica,andorganic coatingstopromotedispersibility,hiding,durability,andphotostability [4].Incoatingapplications,surfacemodificationisperformedalsotoimprovechalkresistance andglossretentioninoutdoorapplications,andtofavorphysicalspacingbetween theparticlesinordertoleadtosuperiorhidingeffect.TiO2 efficientlyscattersvisibleandinfraredradiationwhileabsorbingUVlight.Thereforeobjectscontaining TiO2 lastlongerespeciallywhenexposedtoweathering,resisttoheatandlight, thusfinallyresultinginlesswasteproduction.Also,themechanicalstabilityofthe coatingsisimprovedinthepresenceofTiO2.Forinstance,TiO2-containingpaints usedinthevehiclesindustrymaterialsincreasestability,persistence,andresistance toscratches [5].Moreover,highbrilliance,colorstrength,andopacitytargetscan beobtainedwithloweramountsofresources.Inthissense,TiO2 contributestocirculareconomyandenvironmentcare,improvingefficiencyandoptimizingtheuse ofresourcesformanyproducts,whicharemaintainedinuseforaslongaspossible, thusreducinggenerationofwastes.TiO2 enablesreuseandrecycleofobjectsat theendoftheirlife,enhancingthelongevityoftheproducts.Asanexample, TitaniumDioxide(TiO2)andItsApplications.DOI: https://doi.org/10.1016/B978-0-12-819960-2.00018-3 © 2021ElsevierInc.Allrightsreserved.
