Developments in Electrochemistry: Science Inspired by Martin Fleischmann

393 Pages·2014·11.797 MB·English

by  Derek Pletcher, Zhong-Qun Tian, David Williams

Developments in
electrochemistry
Science Inspired by Martin Fleischmann

Derek Pletcher • Zhong-Qun Tian • David E. Williams
Editors:

Developments in Electrochemistry

Developments in
Electrochemistry
Science Inspired by Martin Fleischmann
Editors
DEREK PLETCHER
Chemistry, University of Southampton, UK
ZHONG-QUN TIAN
State Key Laboratory of Physical Chemistry of Solid Surfaces,
Xiamen University, China
DAVID E. WILLIAMS
School of Chemical Sciences, University of Auckland, New Zealand
Thiseditionfirstpublished2014
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Contents
ListofContributors xiii
1 MartinFleischmann–TheScientistandthePerson 1
2 ACriticalReviewoftheMethodsAvailableforQuantitativeEvaluationof
ElectrodeKineticsatStationaryMacrodiskElectrodes 21
AlanM.Bond,ElenaA.MashkinaandAlexandrN.Simonov
2.1 DCCyclicVoltammetry 23
2.1.1 Principles 23
2.1.2 ProcessingDCCyclicVoltammetricData 26
2.1.3 Semiintegration 29
2.2 ACVoltammetry 32
2.2.1 AdvancedMethodsofTheory–ExperimentComparison 35
2.3 ExperimentalStudies 36
2.3.1 Reductionof[Ru(NH ) ]3+inanAqueousMedium 36
3 6
2.3.2 OxidationofFeII(C H ) inanAproticSolvent 40
5 5 2
2.3.3 Reductionof[Fe(CN) ]3−inanAqueousElectrolyte 42
6
2.4 ConclusionsandOutlook 43
References 45
3 Electrocrystallization:ModelingandItsApplication 49
MortezaY.Abyaneh
3.1 ModelingElectrocrystallizationProcesses 53
3.2 ApplicationsofModels 56
3.2.1 TheDepositionofLeadDioxide 58
3.2.2 TheElectrocrystallizationofCobalt 60
3.3 SummaryandConclusions 61
References 63
4 NucleationandGrowthofNewPhasesonElectrodeSurfaces 65
BenjaminR.ScharifkerandJorgeMostany
4.1 AnOverviewofMartinFleischmann’sContributionstoElectrochemical
NucleationStudies 66
4.2 ElectrochemicalNucleationwithDiffusion-ControlledGrowth 67
vi Contents
4.3 MathematicalModelingofNucleationandGrowthProcesses 68
4.4 TheNatureofActiveSites 69
4.5 InductionTimesandtheOnsetofElectrochemicalPhase
FormationProcesses 71
4.6 Conclusion 72
References 72
5 OrganicElectrosynthesis 77
DerekPletcher
5.1 IndirectElectrolysis 79
5.2 IntermediatesforFamiliesofReactions 80
5.3 SelectiveFluorination 84
5.4 Two-PhaseElectrolysis 85
5.5 ElectrodeMaterials 87
5.6 TowardsPharmaceuticalProducts 88
5.7 FutureProspects 90
References 91
6 ElectrochemicalEngineeringandCellDesign 95
FrankC.WalshandDerekPletcher
6.1 PrinciplesofElectrochemicalReactorDesign 96
6.1.1 CellPotential 96
6.1.2 TheRateofChemicalChange 97
6.2 DecisionsDuringtheProcessofCellDesign 98
6.2.1 StrategicDecisions 98
6.2.2 DividedandUndividedCells 98
6.2.3 MonopolarandBipolarElectricalConnectionstoElectrodes 99
6.2.4 ScalingtheCellCurrent 100
6.2.5 Porous3DElectrodeStructures 100
6.2.6 InterelectrodeGap 101
6.3 TheInfluenceofElectrochemicalEngineeringonthe
Chlor-AlkaliIndustry 102
6.4 ParallelPlateCells 105
6.5 RedoxFlowBatteries 106
6.6 RotatingCylinderElectrodeCells 107
6.7 Conclusions 108
References 109
7 ElectrochemicalSurface-EnhancedRamanSpectroscopy(EC-SERS):
EarlyHistory,Principles,Methods,andExperiments 113
Zhong-QunTianandXue-MinZhang
7.1 EarlyHistoryofElectrochemicalSurface-Enhanced
RamanSpectroscopy 116
Contents vii
7.2 PrinciplesandMethodsofSERS 117
7.2.1 ElectromagneticEnhancementofSERS 118
7.2.2 KeyFactorsInfluencingSERS 119
7.2.3 “BorrowingSERSActivity”Methods 121
7.2.4 Shell-IsolatedNanoparticle-EnhancedRamanSpectroscopy 123
7.3 FeaturesofEC-SERS 124
7.3.1 ElectrochemicalDoubleLayerofEC-SERSSystems 124
7.3.2 ElectrolyteSolutionsandSolventDependency 125
7.4 EC-SERSExperiments 125
7.4.1 MeasurementProceduresforEC-SERS 125
7.4.2 ExperimentalSet-UpforEC-SERS 127
7.4.3 PreparationofSERSSubstrates 128
Acknowledgments 131
References 131
8 ApplicationsofElectrochemicalSurface-EnhancedRaman
Spectroscopy(EC-SERS) 137
MarcoMusiani,Jun-YangLiuandZhong-QunTian
8.1 PyridineAdsorptiononDifferentMetalSurfaces 138
8.2 InterfacialWateronDifferentMetals 141
8.3 CoadsorptionofThioureawithInorganicAnions 143
8.4 ElectroplatingAdditives 146
8.5 InhibitionofCopperCorrosion 147
8.6 ExtensionofSERStotheCorrosionofFeandItsAlloys:Passivity 149
8.6.1 Fe-on-Ag 150
8.6.2 Ag-on-Fe 150
8.7 SERSofCorrosionInhibitorsonBareTransitionMetalElectrodes 150
8.8 LithiumBatteries 152
8.9 IntermediatesofElectrocatalysis 154
Acknowledgments 156
References 156
9 In-SituScanningProbeMicroscopies:ImagingandBeyond 163
Bing-WeiMao
9.1 PrincipleofIn-SituSTMandIn-SituAFM 164
9.1.1 PrincipleofIn-SituSTM 164
9.1.2 PrincipleofIn-SituAFM 166
9.2 In-SituSTMCharacterizationofSurfaceElectrochemicalProcesses 167
9.2.1 In-SituSTMStudyofElectrode–AqueousSolutionInterfaces 167
9.2.2 In-SituSTMStudyofElectrode–IonicLiquidInterface 167
9.3 In-SituAFMProbingofElectricDoubleLayer 170
9.4 ElectrochemicalSTMBreak-JunctionforSurfaceNanostructuringand
NanoelectronicsandMolecularElectronics 173
9.5 Outlook 176
References 177
viii Contents
10 In-SituInfraredSpectroelectrochemicalStudiesoftheHydrogen
EvolutionReaction 183
RichardJ.Nichols
10.1 TheH+/H Couple 183
2
10.2 Single-CrystalSurfaces 184
10.3 SubtractivelyNormalizedInterfacialFourierTransform
InfraredSpectroscopy 186
10.4 Surface-EnhancedRamanSpectroscopy 189
10.5 Surface-EnhancedIRAbsorptionSpectroscopy 190
10.6 In-SituSumFrequencyGenerationSpectroscopy 193
10.7 SpectroscopyatSingle-CrystalSurfaces 194
10.8 OverallConclusions 197
References 198
11 ElectrochemicalNoise:APowerfulGeneralTool 201
ClaudeGabrielliandDavidE.Williams
11.1 Instrumentation 202
11.2 Applications 204
11.2.1 ElementaryPhenomena 204
11.2.2 Bioelectrochemistry 205
11.2.3 Electrocrystallization 207
11.2.4 Corrosion 209
11.2.5 OtherSystems 215
11.3 Conclusions 217
References 217
12 FromMicroelectrodestoScanningElectrochemicalMicroscopy 223
SalvatoreDanieleandGuyDenuault
12.1 TheContributionofMicroelectrodestoElectroanalyticalChemistry 224
12.1.1 AdvantagesofMicroelectrodesinElectroanalysis 224
12.1.2 MicroelectrodesandElectrodeMaterials 226
12.1.3 NewApplicationsofMicroelectrodesinElectroanalysis 227
12.2 ScanningElectrochemicalMicroscopy(SECM) 230
12.2.1 ABriefHistoryofSECM 230
12.2.2 SECMwithOtherTechniques 231
12.2.3 TipGeometriesandtheNeedforNumericalModeling 233
12.2.4 ApplicationsofSECM 234
12.3 Conclusions 235
References 235
13 ColdFusionAfterAQuarter-Century:ThePd/DSystem 245
MelvinH.MilesandMichaelC.H.McKubre
13.1 TheReproducibilityIssue 247
13.2 Palladium–DeuteriumLoading 247