Heterogeneous Photocatalysis: From Fundamentals to Applications in Energy Conversion and Depollution

366 Pages·2021·11.213 MB·English

by  Jennifer Strunk (editor)

HeterogeneousPhotocatalysis
Heterogeneous Photocatalysis
From Fundamentals to Applications in Energy Conversion
and Depollution
Edited by
Jennifer Strunk
Editor AllbookspublishedbyWILEY-VCH
arecarefullyproduced.Nevertheless,
Prof.Dr.JenniferStrunk authors,editors,andpublisherdonot
LeibnizInstituteforCatalysis warranttheinformationcontainedin
DepartmentofHeterogeneous thesebooks,includingthisbook,to
Photocatalysis befreeoferrors.Readersareadvised
Albert-Einstein-Str.29a tokeepinmindthatstatements,data,
18059Rostock illustrations,proceduraldetailsorother
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v
Contents
Preface xi
1 KineticandThermodynamicConsiderationsforPhotocatalyst
Design 1
FrankE.Osterloh
1.1 Introduction 1
1.2 MechanisticAspectsofPhotochemicalReactionSystems 2
1.3 CommonParametersofPhotochemicalReactionSystems 10
1.4 DifferencesBetweenPhotocatalyticandPhotosyntheticReaction
Systems 13
1.5 Conclusion 17
Acknowledgment 18
References 18
2 DesignofReliableStudiesonPhotocatalysis:Logic,Concepts,
andMethods 29
BunshoOhtani
2.1 Photocatalysis 29
2.2 ReliabilityinScientificStudies 30
2.2.1 ReliabilityinScience 30
2.2.2 TruthinScience:UnambiguousnessText 30
2.2.3 LogicinScientificStudies 30
2.2.4 ExamplesofPropositions 31
2.2.5 Counter(Contrary)Evidence:KillerCard 32
2.2.6 ReliabilityinScientificStudies 34
2.3 MethodsinPhotocatalysisStudies 34
2.3.1 BandgapDeterminationbyTaucPlots 34
2.3.2 ActionSpectrumAnalysis 36
2.3.3 LightIntensity-DependentAnalysis 39
2.3.4 PhotocatalyticActivityEvaluation 41
vi Contents
2.3.5 CorrelationBetweenPhotocatalyticActivityandPhysical/Structural
Properties 44
2.4 DesignofReliableStudiesonPhotocatalysis 46
References 46
3 InSituSpectroscopyforMechanisticStudiesinSemiconductor
Photocatalysis 51
JanP.Hofmann
3.1 Introduction 51
3.2 ChallengesinInSituandOperandoCharacterizationin
Photocatalysis 52
3.3 OverviewofMethodsandExamplesfromtheLiterature 54
3.3.1 (Transient)UV/Vis/NIRElectronicSpectroscopies 57
3.3.2 VibrationalSpectroscopies 59
3.3.2.1 InfraredSpectroscopy 59
3.3.2.2 RamanSpectroscopyandMicroscopy 63
3.3.2.3 NonlinearSpectroscopies:Second-harmonicGenerationandSum
FrequencyGenerationSpectroscopies 64
3.3.3 ElectronParamagneticResonance 65
3.3.4 (Synchrotron)X-raySpectroscopies 66
3.3.4.1 PhotoelectronSpectroscopy 66
3.3.4.2 X-rayAbsorptionSpectroscopy(XAS,XANES,andEXAFS) 68
3.4 OutlookandFuturePerspectives 68
References 69
4 PrinciplesandLimitationsofPhotoelectrochemicalFuel
Generation 77
BastianMeiandKasperWenderich
4.1 Introduction 77
4.2 PhotoelectrochemicalEnergyStorage 78
4.2.1 ThermodynamicRequirementsandDrivingForces 78
4.2.2 BasicsofSemiconductorsandtheSemiconductor/Electrolyte
Interface 80
4.2.3 Semiconductor/ElectrolyteInterfaceUnderIllumination 84
4.2.4 DevicesandEfficiencies 86
4.2.4.1 DeviceConfigurations 86
4.2.4.2 DeviceFiguresofMeritandSystemEfficiencies 87
4.2.4.3 TheoreticalLimitationsofPECSolarFuelProduction 90
4.2.4.4 TheoreticalLimitationsofPECSolarFuelProduction–BeyondWater
Splitting 93
4.2.5 SurfaceModification 94
4.2.5.1 IntegrationofElectrocatalysts 95
4.2.5.2 StabilityofPECDevice–ProtectionLayers/SurfaceCoatings 96
4.2.6 ShortSummary 97
References 98
Contents vii
5 Photocatalysis–TheHeterogeneousCatalysis
Perspective 101
PawelNaliwajkoandJenniferStrunk
5.1 Introduction 101
5.1.1 GeneralFunctionofClassicalHeterogeneousCatalysts 102
5.1.2 ComparisonofClassicalCatalysisandPhotocatalysis 103
5.2 ExamplesofRelevantCatalyticPropertiesofPhotocatalysts 109
5.2.1 ConsiderationofActiveSites 109
5.2.2 NanosizedGoldinAlcoholOxidation 109
5.2.3 VanadiumOxide(Sub)monolayerCatalystsinPhotocatalyticAlcohol
Oxidation 113
5.3 Conclusions 117
References 118
6 InsightsintoPhotocatalysisfromComputational
Chemistry 127
StephenRhatiganandMichaelNolan
6.1 Introduction 127
6.2 ComputationalDescriptors 128
6.2.1 LightAbsorption 128
6.2.2 ChargeCarrierSeparation 130
6.2.3 SurfaceReactivity 134
6.3 ExamplesofComputationalStudiesofPhotocatalystMaterials 138
6.3.1 MetalOxides 138
6.3.2 NobleMetalLoading 139
6.3.3 MetalChalcogenidesandMetalPhosphides 142
6.3.4 Hetero-andNanostructuring 144
6.3.5 ChargeLocalizationModels 146
6.4 Conclusion 147
References 149
7 SelectedAspectsofPhotoreactorEngineering 155
DirkZiegenbalg
7.1 FundamentalsofPhotochemicalReactionEngineering 155
7.2 RadiationFieldandRateofReaction 160
7.3 LightSources 166
7.4 ParticularitiesofDifferentTypesofPhotocatalysts 173
7.5 TypesofPhotoreactors 176
7.6 ConclusionsandOutlook 181
SymbolsandAbbreviations 182
References 184
8 DefectsinPhotocatalysis 187
GretaHaselmannandDominikEder
8.1 Introduction 187
8.1.1 DefinitionandThermodynamics 187
viii Contents
8.1.2 Classification 188
8.1.2.1 Dimensionality 188
8.1.2.2 Location:Surface,Subsurface,andBulk 189
8.1.3 ConceptsinDefectChemistry 190
8.1.3.1 ChargeNeutrality 190
8.1.3.2 IntrinsicandExtrinsicDefectPairs 190
8.1.3.3 Nonstoichiometryvs.Substoichiometry 190
8.1.3.4 Kröger–VinkNotationandDefectDiagrams 191
8.1.3.5 DiffusionandSegregation 192
8.1.4 HowAreDefectsCreated? 192
8.1.4.1 IntrinsicDefects 192
8.1.4.2 ExtrinsicDefects 193
8.1.5 CharacterizationofDefects 194
8.1.5.1 Quantification 196
8.1.5.2 InSitu 196
8.1.6 EffectofDefectsonMaterialProperties 197
8.1.6.1 StructuralChanges/PhysicalStructure 197
8.1.6.2 ElectronicChanges/ElectronicStructure 197
8.2 InfluenceofDefectsonthePhotocatalyticPerformance 199
8.2.1 LocationoftheDefect 200
8.2.1.1 Bulk:ChargeCarrierGenerationandMigration 200
8.2.1.2 Surface:AdsorptionSitesandChargeTransfer 202
8.2.1.3 OptimizedTreatmentConditionsandSurface-to-bulkRatio 204
8.2.1.4 SubsurfaceDefectsinPhotocatalysis 206
8.2.2 Deepvs.ShallowTrapStates 206
8.2.3 Strain-InducedPhotocatalysis 207
8.2.4 DynamicDefects 208
8.2.5 DefectsofHigherDimensionalitiesinPhotocatalysis 208
8.2.5.1 BlackTiO 210
2
8.3 ConcludingRemarks 213
References 213
9 PhotocarrierLossPathwaysinMetalOxideAbsorberMaterials
forPhotocatalysisExploredwithTime-Resolved
Spectroscopy:TheCaseofBiVO 221
4
RainerEichbergerandSönkeMüller
9.1 Introduction 221
9.2 PhotodynamicsofBiVO –CarrierTrappingandPolaron
4
Formation 224
9.3 Conclusions 238
References 238
10 Metal-freePhotocatalysts 245
JosefineP.Hundt,MarcoWeers,VanessaLührs,DerejeH.Taffa,andMichael
Wark
10.1 Introduction 245
10.2 GraphiticCarbonNitrides 246
Contents ix
10.2.1 StructureandPropertiesofg-C N 246
3 4
10.2.2 ApplicationasPhotocatalyticActiveMaterial 249
10.2.2.1 PhotocatalyticHydrogenProduction 249
10.2.2.2 Photocatalysis-AssistedOrganicSynthesis 250
10.2.2.3 PhotocatalyticReductionofCO 252
2
10.2.2.4 PhotocatalyticDegradationof(Organic)Pollutants 254
10.3 CovalentOrganicFrameworks 254
10.4 ConjugatedPolymers 257
10.4.1 SynthesisStrategiesofNanostructuredConductingPolymers 258
10.4.2 ApplicationasaPhotocatalyticActiveMaterial 260
10.4.2.1 HydrogenEvolution 261
10.4.2.2 PollutantDegradation 261
10.5 Conclusions 263
Acknowledgments 264
References 264
11 PhotocatalyticWaterSplitting:FundamentalsandCurrent
Concepts 269
KazuhiroTakanabe
11.1 SolarEnergyConversion 269
11.2 Photocatalyst:FundamentalConcept 270
11.3 ReportingProtocol 272
11.4 PhotonAbsorption 276
11.5 ExcitonSeparation 276
11.6 CarrierTransport 277
11.7 Electrocatalysis 279
11.8 MassTransfer:Electrolyte 280
11.9 SuppressionofBackReaction 280
11.10 PhotocatalyticOverallWaterSplitting:StateoftheArt 281
11.11 ConcludingRemarks 283
References 284
12 PhotocatalyticCO ReductionandBeyond 287
2
MinooTasbihi,MichaelSchwarze,andReinhardSchomäcker
12.1 Introduction 287
12.2 PhotocatalyticReactionsUtilizingCO 290
2
12.2.1 PhotocatalyticReductionofCO byCH (DryReforming) 292
2 4
12.2.2 PhotocatalyticReductionofCO byCH andH O(Steam
2 4 2
Reforming) 296
12.2.3 OtherPhotocatalyticReactionswithCO 298
2
12.3 Summary 298
References 299
13 PhotocatalyticNO Abatement 303
x
JonathanZ.Bloh
13.1 Introduction 303
13.2 BasicPrinciple 304
x Contents
13.3 ReactionPathway 305
13.3.1 Intermediates,Selectivity 307
13.4 ReactionKinetics 308
13.4.1 GuidelinesforAccuratePerformanceDetermination 310
13.5 StrategiestoImprovethePerformance 312
13.5.1 StrategiestoImprovethePhotocatalyticActivity 312
13.5.2 StrategiestoImprovetheSpectralResponse 314
13.5.3 StrategiestoImprovetheSelectivity 317
13.5.4 SummaryofMaterialDevelopments 319
13.6 StrategiestoIncorporatetheCatalystsintoBuildingMaterials 319
13.7 ResultsfromFieldTestsandSimulations 321
References 323
14 PhotoactiveNanomaterials:ApplicationsinWastewater
TreatmentandTheirEnvironmentalFate 331
JangS.ChangandMengN.Chong
14.1 Introduction 331
14.2 PhotoactiveSemiconductorNanomaterialsandTheirApplicationsin
WastewaterTreatment 332
14.2.1 Nano-TiO 332
2
14.2.2 Nano-ZnO 334
14.2.3 Nano-Fe O 336
2 3
14.2.4 Nano-WO 337
3
14.3 EnvironmentalFateandBehaviorofPhotoactiveNanomaterialsin
WastewaterTreatmentProcesses 338
14.3.1 Prevalence,Occurrence,andRoutesofNanomaterialsintothe
Environment 338
14.3.2 FateandTransformationProcessesofNanomaterials 339
14.3.2.1 AggregationandAgglomeration 339
14.3.2.2 PhotochemicalTransformation 342
14.3.2.3 RedoxReactions 342
14.3.2.4 AdsorptionofMacromolecules 343
14.3.2.5 Biotransformation 344
14.4 EnvironmentalEffectsofNanomaterialsTowardWastewaterTreatment
Processes 344
14.5 Conclusion 345
References 346
Index 351
xi
Preface
Itseemssosimple:Takeabeakerandshinelightonit.ThisisanopinionIhavecome
acrossoccasionallysincestartingtoworkinthefieldofphotocatalysisprettymuch
exactly10yearsago.Indeed,itmaybeonewaytostart.However,ifoneisactivein
thisresearchfieldforawhile,itwillbeunavoidabletofacehighlycomplexquestions
thatcanonlybeappropriatelyaddressedwithbroadinterdisciplinaryexpertise.My
ownstartingpointwasclassicalheterogeneouscatalysis,butotherresearchersenter
thefieldofphotocatalysiswithabackgroundinelectrochemistry,materialscience,
orsemiconductorphysics,tonamejustafew.Ifirmlybelievethatbycombination
of the different viewpoints, the toolbox of photocatalysis can be fully exploited to
developthesolutionsforsustainableenergyconversionandenvironmentaldepol-
lutiontheworldsodearlyneeds.Inthissense,itisthepurposeofthisbooktopave
thewaytowardmutualunderstanding.Researchersnewtothefieldofphotocataly-
siscanacquirebasicknowledgeinthoseresearchareasstillunfamiliartothem.Istill
remembermyearlydays,whenIspentmuchtimesearchingforliteratureonelec-
trochemistryrelevantformyresearch.Therefore,Iwantedtoprovideabookwhere
allthemostimportantfundamentalsfromallfieldscanbefoundinoneplace.Expe-
riencedphotocatalysisresearcherswillbeabletousethisbooknotonlyinteaching
but also to get an overview over the state of the art in the various target applica-
tions.Inadditiontoreviewingthenumerousrecentscientificarticlesintheirfield,
allthechapterauthorswantedtogainandsharenewknowledgebycombiningthe
variousstudiesintoaunifiedpicture.Isincerelyhopethatnewinsightsandideas
willemergefromthisendeavor.
Please allow me to express my deepest gratitude to all my international expert
colleagueswhocontributedtheirvaluablespecialistexpertisetosuccessfullycover
awiderangeoftopics.Andnoless,IwouldliketothankeveryoneatWiley-VCHfor
makingthisbookpossible.
Rostock,18October2020 JenniferStrunk