Single Particle Nanocatalysis Fundamentals and Applications

304 Pages·2019·10.192 MB·English

by  Chen, Tao, Xu, Weilin, Zhang, Yuwei

SingleParticleNanocatalysis

Single Particle Nanocatalysis
FundamentalsandApplications
WeilinXu,YuweiZhang,andTaoChen
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Prof.YuweiZhang
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v
Contents
Preface xi
1 TheHistory/DevelopmentofSingleParticleNanocatalysis 1
1.1 HistoryofSingleParticleNanocatalysisBasedonSingleMolecule
FluorescenceMicroscopy 2
1.2 HistoryofSingleParticleNanocatalysisBasedon(Localized)Surface
PlasmonResonance 3
1.3 HistoryofSingleParticleNanocatalysisBasedonScanning
ElectrochemicalMicroscopy 4
1.4 HistoryofSingleParticleNanocatalysisBasedonVibrational
Spectroscopies 5
References 6
2 SingleMoleculeNanocatalysisRevealsCatalyticKineticsand
ThermodynamicsofIndividualNanocatalysts 9
2.1 SingleMoleculeEnzymology 9
2.1.1 SingleMoleculeMichaelis–MentenKineticsintheAbsenceof
DynamicDisorder 9
2.1.2 SingleMoleculeMichaelis–MentenKineticswithDynamic
Disorder 13
2.1.3 RandomnessParameter 20
2.1.4 SingleMoleculeMichaelis–MentenKineticsforFluorogenicReaction
intheAbsenceofDynamicDisorder 21
2.2 PhysicalModelsforKineticandDynamicAnalysisofSingleMolecule
Nanocatalysts 23
2.2.1 Langmuir–HinshelwoodMechanismforNoncompetitive
HeterogeneousCatalysis 23
2.2.1.1 Langmuir–HinshelwoodMechanismforProductFormation 24
2.2.1.2 Two-PathwayModelforProductionDissociation 27
2.2.1.3 OverallTurnoverRate 29
2.2.2 Langmuir–HinshelwoodMechanismforCompetitiveHeterogeneous
Catalysis 30
2.3 ComparisonBetweenMichaelis–MentenMechanismand
NoncompetitiveLangmuir–HinshelwoodMechanism 31
vi Contents
2.4 Michaelis–MentenMechanismCoupledwithMultipleProduct
DissociationPathways 32
2.4.1 ProductDissociationProcess 32
2.4.2 ProductFormationProcess 33
2.5 ApplicationofLangmuir–HinshelwoodMechanismtoOligomeric
Enzymes 35
2.6 ApplicationsofCompetitive/NoncompetitiveLangmuir–Hinshelwood
ModelsinSingleMoleculeNanocatalysis 35
2.6.1 ApplicationsofNoncompetitiveLangmuir–HinshelwoodModelsin
SingleMoleculeNanocatalysis 35
2.6.1.1 SingleMoleculeNanocatalysisonSingleAuNanoparticles 35
2.6.1.2 SingleMoleculePhotocatalysisonSingleTiO Nanoparticles 38
2
2.6.2 ApplicationsofCompetitiveLangmuir–HinshelwoodModelsinSingle
MoleculeNanocatalysis 41
2.6.2.1 SinglePtNanocatalystBehavesDifferentlyinDifferentReactions 41
2.6.2.2 SingleMoleculeNanocatalysisatSubparticleLevel 42
2.7 SingleMoleculeNanocatalysisRevealstheCatalyticThermodynamics
ofSingleNanocatalysts 44
Abbreviation 46
References 46
3 CombinationofTraditionalSMFMwithOtherTechniquesfor
SingleMolecule/ParticleNanocatalysis 49
3.1 IntroductionofSMFM-BasedSingleParticleNanocatalysisAnalysis
Method 49
3.2 SMFMCombiningwithElectrochemicalTechniques 49
3.3 SMFMCombiningwithAFM 57
3.4 Conclusion 60
Abbreviations 60
References 60
4 OpticalSuper-ResolutionImaginginSingleMolecule
Nanocatalysis 63
4.1 HistoryandPrincipleofDifferentOpticalSuper-Resolution(SR)
Techniques 63
4.1.1 HistoryofOpticalSuper-Resolution(SR)Techniques 63
4.1.2 PrincipleofOpticalSuper-Resolution(SR)Imaging 65
4.1.2.1 Super-ResolutionImagingwithSpatiallyPatternedExcitation 65
4.1.2.2 LocalizationMicroscopy:Super-ResolutionImagingBasedonSingle
MoleculeLocalization 66
4.2 ApplicationofSuper-ResolutionImaginginSingleParticle
Catalysis 68
4.2.1 LayeredDoubleHydroxide(LDH) 69
4.2.2 Zeolites 69
4.2.2.1 Super-ResolutionImagingonZeolites 69
4.2.2.2 DepthProfilingwithSuper-ResolutionImagingonZeolites 74
Contents vii
4.2.3 MetalNanoparticles 76
4.2.4 SupportedMetalNanocatalysts 79
4.2.5 SemiconductorsasPhoto(electro)catalysts 80
4.2.5.1 ActiveSite/FacetMapping 82
4.2.5.2 PhotogeneratedChargeSeparation 82
4.2.5.3 DesignaPhoto(electro)catalyst 84
4.2.6 Electrocatalysts 86
4.2.7 ImagingtheChemicalReactions 87
4.2.7.1 KineticStudiesofSingleMoleculeFluorogenicReactions 87
4.2.7.2 SRImagingoftheSingleMoleculeReactionsonDifferentSurfaces 89
4.2.8 OtherApplicationsofSRImagingTechnique 91
4.3 Summary 92
Abbreviations 92
References 93
5 ScanningElectrochemicalMicroscopy(SECM)forSingle
ParticleNanocatalysis 107
5.1 BriefReviewofScanningElectrochemicalMicroscopy(SECM) 107
5.2 PrinciplesofSECM 109
5.2.1 PreparationofNanoelectrodes 111
5.2.1.1 FabricationMethod1:ElectronBeamLithography 111
5.2.1.2 FabricationMethod2:Glass-CoatedElectrode 113
5.2.2 OperationModesofSECM 113
5.2.2.1 CollectionMode 113
5.2.2.2 FeedbackMode 117
5.3 PreparationofSingleNanoparticleSamplesforElectrocatalytic
Studies 118
5.3.1 “Jump-to-contact”MethodforPreparingSingleNanoparticlesBased
onTip-InducedDepositionofMetal 119
5.3.2 ElectrochemicalMethodsofPreparingandCharacterizing
Single-MetalNPs 120
5.3.2.1 DirectElectrodepositingofSingle-MetalNPsonaMacroscopic
Substrate 121
5.3.2.2 MechanicalTransferoftheNanoparticlefromtheTip 123
5.3.2.3 AnodizationofTipMaterial 124
5.3.2.4 Single-NanoparticleFormationonUltramicroscopicSubstrate 124
5.3.3 DeterminingElectroactiveRadiioftheSubstrate 125
5.4 ExamplesofTypicalExperimentalDataAnalysisProcess 127
5.4.1 PtNPs/CUME/ProtonReduction 128
5.4.2 WaterOxidationonIrO NP 130
x
5.4.3 HydrogenEvolutionReaction(HER)atthePdNP 133
5.4.4 ScreeningofORRCatalysts 137
5.5 Summary 141
Abbreviations 141
References 142
viii Contents
6 SurfacePlasmonResonanceSpectroscopyforSingleParticle
Nanocatalysis/Reaction 145
6.1 Bulk,Surface,andLocalizedSurface(Nanoparticle)Plasmons 145
6.2 SPRonSingleParticleCatalysisatSingleParticleLevel 146
6.2.1 PrincipleofSPRSensing 146
6.2.2 ExperimentalMethodofSPRonSingleParticleCatalysis 149
6.2.3 Application:ElectrocatalysisofSinglePtNanoparticlesBasedon
SPR 150
6.3 LSPRonSingleParticleCatalysis/ReactionatSingleParticle
Level 150
6.3.1 PrincipleofLSPRSensing 150
6.3.1.1 ElectronInjectionandSpillover 152
6.3.1.2 PlasmonCoupling 153
6.3.1.3 PlasmonResonanceEnergyTransfer 153
6.3.2 ExperimentalMethodofLSPRonSingleParticleCatalysis 154
6.3.2.1 Dark-fieldMicroscopy 154
6.3.2.2 ExperimentalStrategies 155
6.3.3 ApplicationofLSPRSpectroscopytoSingleParticle
Catalysis/Reaction 156
6.3.3.1 Application1:DirectObservationoftheChangesoftheSingle
NanoparticleItself 156
6.3.3.2 Application2:DirectObservationofSurfaceCatalyticReactionson
SingleGoldNanoparticlesbySingleParticleLSPRSpectroscopy 159
6.3.3.3 Application3:IndirectObservationofCatalyticReactionsby
Single-NanoparticleLSPRSpectroscopy 161
6.3.3.4 Application4:IndirectObservationofChemicalReactionsbyPlasmon
ResonanceEnergyTransfer 165
6.3.3.5 Application5:ObservationofElectrochemical/CatalyticReactionson
SingleGoldNanoparticlesbySingleParticleLSPRSpectroscopy 166
Abbreviations 174
References 175
7 X-ray-BasedMicroscopyofSingleParticleNanocatalysis 181
7.1 HistoryofX-rayMicroscopy 181
7.1.1 HistoryoftheSetupsforX-rayAbsorptionFineStructure
(XAFS) 182
7.1.2 EvolutionofX-raySourceBasedonSynchrotronLightSources 185
7.2 ApparatusforMicrometer-ResolvedXAFSSpectroscopy 186
7.2.1 SoftX-raysandHardX-rays 187
7.2.2 Microprobes 188
7.2.3 HowtheX-rayBeamisShaped? 191
7.2.3.1 X-rayBeamOptimization:EnergySelection 192
7.2.3.2 X-rayBeamOptimization:HarmonicRejection 194
7.3 SpatiallyResolvedX-rayMicroprobeMethods 196
7.3.1 Full-FieldTransmissionX-rayMicroscopy(TXM) 196
7.3.2 ZernikePhaseContrastX-rayMicroscopy 197
7.3.3 ScanningTransmissionX-rayMicroscopy(STXM) 198