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 ©2014JohnWiley&Sons,Ltd Registeredoffice JohnWiley&SonsLtd,TheAtrium,SouthernGate,Chichester,WestSussex,PO198SQ,UnitedKingdom Fordetailsofourglobaleditorialoffices,forcustomerservicesandforinformationabouthowtoapplyforpermissiontoreuse thecopyrightmaterialinthisbookpleaseseeourwebsiteatwww.wiley.com. TherightoftheauthortobeidentifiedastheauthorofthisworkhasbeenassertedinaccordancewiththeCopyright,Designs andPatentsAct1988. 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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