Edited by Pierre Pichat Photocatalysis and Water Purification

422 Pages·2013·3.5 MB·English

Editedby
PierrePichat
PhotocatalysisandWater
Purification
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Edited by Pierre Pichat
Photocatalysis and Water Purification
From Fundamentals to Recent Applications
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V
Editorial Board
Members of the Advisory Board of the ‘‘Materials for Sustainable Energy and
Development’’Series
ProfessorHuimingCheng
ProfessorCalumDrummond
ProfessorMorinobuEndo
ProfessorMichaelGra¨tzel
ProfessorKevinKendall
ProfessorKatsumiKaneko
ProfessorCanLi
ProfessorArthurNozik
ProfessorDetlevSto¨ver
ProfessorFerdiSchu¨th
ProfessorRalphYang
VII
Contents
SeriesEditorPreface XVII
Preface XIX
AbouttheSeriesEditor XXIII
AbouttheVolumeEditor XXV
ListofContributors XXVII
PartI Fundamentals:ActiveSpecies,Mechanisms,Reaction
Pathways 1
1 IdentificationandRolesoftheActiveSpeciesGeneratedonVarious
Photocatalysts 3
YoshioNosakaandAtsukoY.Nosaka
1.1 KeySpeciesinPhotocatalyticReactions 3
1.2 TrappedElectronandHole 6
•−
1.3 SuperoxideRadicalandHydrogenPeroxide(O andH O ) 7
2 2 2
•
1.4 HydroxylRadical(OH ) 9
1.5 SingletMolecularOxygen(1O ) 12
2
1.6 ReactionMechanismsforBareTiO 15
2
1.7 ReactionMechanismsofVisible-Light-ResponsivePhotocatalysts 17
1.8 Conclusion 20
References 21
2 PhotocatalyticReactionPathways–EffectsofMolecularStructure,
Catalyst,andWavelength 25
WilliamS.Jenks
2.1 Introduction 25
2.2 MethodsforPathwayDetermination 27
2.3 PrototypicalOxidativeReactivityinPhotocatalyticDegradations 29
2.3.1 OxidationofArenesandtheImportanceofAdsorption 30
2.3.1.1 HydroxylationandtheSourceofOxygen 30
2.3.1.2 Ring-OpeningReactions 32
VIII Contents
2.3.1.3 IndicatorsofSETversusHydroxylChemistryinAromatic
Systems 32
2.3.2 CarboxylicAcids 35
2.3.3 AlcoholFragmentationandOxidation 36
2.3.4 OxidationofAlkylSubstituents 37
2.3.5 ApparentHydrolysisReactions 38
2.3.6 Sulfur-BearingCompounds 39
2.4 PrototypicalReductiveReactivityinPhotocatalyticDegradations 39
2.5 TheUseofOrganicMoleculesasTestProbesforNext-Generation
Photocatalysts 41
2.6 ModifiedCatalysts:Wavelength-DependentChemistryofOrganic
Probes 42
2.7 Conclusions 44
References 45
3 PhotocatalyticMechanismsandReactionPathwaysDrawnfromKinetic
andProbeMolecules 53
ClaudioMinero,ValterMaurino,andDavideVione
3.1 ThePhotocatalyicRate 53
3.1.1 OtherKineticModels 55
3.1.2 Substrate-MediatedRecombination 57
3.2 SurfaceSpeciation 60
3.2.1 DifferentCommercialCatalysts 60
3.2.2 SurfaceManipulation 61
3.2.3 CrystalFaces 62
3.2.4 SurfaceTrapsforHoles 64
3.3 MultisiteKineticModel 65
3.4 Conclusion 68
References 68
PartII ImprovingthePhotocatalyticEfficacy 73
4 DesignandDevelopmentofActiveTitaniaandRelated
Photocatalysts 75
BunshoOhtani
4.1 Introduction–aThermodynamicAspectofPhotocatalysis 75
4.2 PhotocatalyticActivity:Reexamination 77
4.3 DesignofActivePhotocatalysts 78
4.4 AConventionalKineticsinPhotocatalysis:First-OrderKinetics 79
4.5 AConventionalKineticsinPhotocatalysis:Langmuir–Hinshelwood
Mechanism 80
4.6 TopicsandProblemsRelatedtoParticleSizeofPhotocatalysts 82
4.7 RecombinationofaPhotoexcitedElectronandaPositiveHole 85
4.8 EvaluationofCrystallinityasaPropertyAffectingPhotocatalytic
Activity 86
Contents IX
4.9 ElectronTrapsasaPossibleCandidateofaRecombinationCenter 87
4.10 DonorLevels–aMeaningofn-TypeSemiconductor 89
4.11 DependenceofPhotocatalyticActivitiesonPhysicalandStructural
Properties 90
4.11.1 CorrelationbetweenPhysicalPropertiesandPhotocatalytic
Activities 90
4.11.2 StatisticalAnalysisofCorrelationbetweenPhysicalPropertiesand
PhotocatalyticActivities–aTrial 92
4.11.3 CommonFeaturesofTitaniaParticleswithHigherPhotocatalytic
Activity 94
4.11.4 HighlyActiveMesoscopicAnataseParticlesofPolyhedralShape 95
4.12 SynergeticEffect 96
4.13 Doping 97
4.14 ConclusiveRemarks 98
Acknowledgments 99
References 99
5 ModifiedPhotocatalysts 103
NuritShaham-WaldmannandYaronPaz
5.1 WhyModifying? 103
5.2 FormsofModification 104
5.3 ModifiedPhysicochemicalProperties 106
5.3.1 CrystallinityandPhaseStability 106
5.3.2 SurfaceMorphology,SurfaceArea,andAdsorption 107
5.3.3 AdsorptionofOxygen 111
5.3.4 ConcentrationofSurfaceOH 111
5.3.5 Specificity 112
5.3.5.1 TiO SurfaceOvercoating 115
2
5.3.5.2 CompositesComprisedofTiO andMetallicNanoislands 116
2
5.3.5.3 DopingwithMetalIonsandOxides 116
5.3.5.4 Utilizingthe‘‘AdsorbandShuttle’’MechanismtoObtain
Specificity 117
5.3.5.5 MesoporousMaterials 119
5.3.5.6 MolecularImprinting 120
5.3.6 Products’Control 122
5.3.6.1 SurfaceModificationbyMolecularImprinting 123
5.3.6.2 CompositesComprisedofTiO andMetallicNanoislands 124
2
5.3.6.3 DopingwithMetalIons 124
5.3.6.4 NonmetallicComposite 125
5.3.6.5 TiO MorphologyandCrystallinePhase 125
2
5.3.7 ReducingDeactivation 125
5.3.8 RecombinationRatesandChargeSeparation 126
5.3.8.1 StructureModification 127
5.3.8.2 Composites–MetalIslands 127
5.3.8.3 CompositesComprisingCarbonaceousMaterials 128
X Contents
5.3.8.4 CompositesComposedofTiO andNonoxideSemiconductors 128
2
5.3.8.5 CompositesComposedofTiO andOtherOxides 129
2
5.3.8.6 DopingwithMetals 131
5.3.8.7 DopingwithNonmetals 132
5.3.9 VisibleLightActivity 132
5.3.10 Charging–Discharging 132
5.3.11 MassTransfer 133
5.3.12 FacilitatingPhotocatalysisinDeaeratedSuspensions 134
Summary 134
References 134
6 ImmobilizationofaSemiconductorPhotocatalystonSolidSupports:
Methods,Materials,andApplications 145
DidierRobert,Vale´rieKeller,andNicolasKeller
6.1 Introduction 145
6.2 ImmobilizationTechniques 147
6.3 Supports 152
6.3.1 Packed-BedPhotocatalyticMaterials 153
6.3.2 MonolithicPhotocatalyticMaterials 155
6.3.3 OpticalFibers 164
6.4 LaboratoryandIndustrialApplicationsofSupported
Photocatalysts 168
6.5 Conclusion 171
References 172
7 WastewaterTreatmentUsingHighlyFunctionalImmobilizedTiO
2
Thin-FilmPhotocatalysts 179
MasayaMatsuoka,TakashiToyao,YuHoriuchi,MasatoTakeuchi,and
MasakazuAnpo
7.1 Introduction 179
7.2 ApplicationofaCascadeFalling-FilmPhotoreactor(CFFP)forthe
RemediationofPollutedWaterandAirunderSolarLight
Irradiation 180
7.3 ApplicationofTiO Thin-Film-CoatedFibersfortheRemediationof
2
PollutedWater 184
7.4 ApplicationofTiO ThinFilmforPhotofuelCells(PFC) 186
2
7.5 PreparationofVisible-Light-ResponsiveTiO ThinFilmsandTheir
2
ApplicationtotheRemediationofPollutedWater 187
7.5.1 Visible-Light-ResponsiveTiO ThinFilmsPreparedbyCationor
2
AnionDoping 188
7.5.2 Visible-Light-ResponsiveTiO ThinFilmsPreparedbytheMagnetron
2
SputteringDepositionMethod 190
7.6 Conclusions 195
References 195
Contents XI
8 SensitizationofTitaniaSemiconductor:APromisingStrategytoUtilize
VisibleLight 199
ZhaohuiWang,ChunchengChen,WanhongMa,andJincaiZhao
8.1 Introduction 199
8.2 PrincipleofPhotosensitization 200
8.3 DyeSensitization 201
8.3.1 FundamentalsofDyeSensitization 202
8.3.1.1 GeometryandElectronicStructureofInterface 202
8.3.1.2 Excited-StateRedoxPropertiesofDyes 203
8.3.1.3 ElectronTransferfromDyestoTiO 205
2
8.3.2 ApplicationofDyeSensitization 208
8.3.2.1 NonregenerativeDyeSensitization 208
8.3.2.2 RegenerativeDyeSensitization 211
8.4 PolymerSensitization 213
8.4.1 CarbonNitridePolymer 213
8.4.2 ConductingPolymers 214
8.5 Surface-Complex-MediatedSensitization 214
8.5.1 OrganicLigand 215
8.5.2 InorganicLigand 217
8.6 SolidSemiconductor/MetalSensitization 218
8.6.1 Small-Band-GapSemiconductor 219
8.6.1.1 BasicConcepts 219
8.6.1.2 CategoryinTermsofChargeTransferProcess 219
8.6.2 PlasmonicMetal 222
8.6.2.1 BasicConcepts 222
8.6.2.2 ProposedMechanisms 224
8.6.2.3 CriticalParameters 225
8.7 OtherStrategiestoMakeTitaniaVisibleLightActive 226
8.7.1 BandGapEngineering 226
8.7.1.1 MetalDoping 226
8.7.1.2 NonmetalDoping 227
8.7.1.3 Codoping 227
8.7.2 Structure/SurfaceEngineering 228
8.8 Conclusions 230
Acknowledgment 231
References 231
9 PhotoelectrocatalysisforWaterPurification 241
RossanoAmadelliandLucaSamiolo
9.1 Introduction 241
9.2 PhotoeffectsatSemiconductorInterfaces 242
9.3 WaterDepollutionatPhotoelectrodes 245
9.3.1 MorphologyandMicrostructure 245
9.3.2 EffectofAppliedPotential 247
9.3.3 EffectofpH 247