Surface and interface science. Volume 8: Interfacial Electrochemistry PDF
Preview Surface and interface science. Volume 8: Interfacial Electrochemistry
Editedby KlausWandelt SurfaceandInterfaceScience SurfaceandInterfaceScience EditedbyKlausWandelt Volume1:ConceptsandMethods Volume2:PropertiesofElementalSurfaces PrintISBN978-3-527-41156-6 oBookISBN978-3-527-68053-5(Volume1) oBookISBN978-3-527-68054-2(Volume2) Volume3:PropertiesofCompositeSurfaces:Alloys,Compounds,Semiconductors Volume4:Solid-SolidInterfacesandThinFilms PrintISBN978-3-527-41157-3 oBookISBN978-3-527-68055-9(Volume3) oBookISBN978-3-527-68056-6(Volume4) Volume5:Solid-GasInterfacesI Volume6:Solid-GasInterfacesII PrintISBN978-3-527-41158-0 oBookISBN978-3-527-68057-3(Volume5) oBookISBN978-3-527-68058-0(Volume6) Volume7:LiquidandBiologicalInterfaces Volume8:InterfacialElectrochemistry PrintISBN978-3-527-41159-7 oBookISBN978-3-527-68059-7(Volume7) oBookISBN978-3-527-68060-3(Volume8) Volume9:ApplicationsofSurfaceScienceI Volume10:ApplicationsofSurfaceScienceII PrintISBN978-3-527-41381-2 oBookISBN978-3-527-82249-2(Volume9) oBookISBN978-3-527-82250-8(Volume10) EditedbyKlausWandelt Surface and Interface Science Volume8:InterfacialElectrochemistry TheEditor AllbookspublishedbyWiley-VCHare Prof.Dr.KlausWandelt carefullyproduced.Nevertheless,authors, UniversityofBonn editors,andpublisherdonotwarrantthe InstituteofPhysicaland informationcontainedinthesebooks, TheoreticalChemistry includingthisbook,tobefreeoferrors. Germany Readersareadvisedtokeepinmindthat and statements,data,illustrations,procedural detailsorotheritemsmayinadvertently UniversityofWroclaw beinaccurate. InstituteofExperimentalPhysics Poland LibraryofCongressCardNo.:appliedfor CoverPictures: BritishLibrary Left:Reprintedwithpermissionfrom Cataloguing-in-PublicationData Morschletal.,J.Phys.Chem.C,2008, Acataloguerecordforthisbookis 112(26),pp9548–9551.Copyright©2008 availablefromtheBritishLibrary. AmericanChemicalSociety. Middle:Kindlyprovided Bibliographicinformationpublishedby byProf.Groß(TUUlm). theDeutscheNationalbibliothek Right:Kindlyprovidedby TheDeutscheNationalbibliothekliststhis Prof.KlausWandelt,UniversityofBonn, publicationintheDeutsche Germany. Nationalbibliografie;detailed bibliographicdataareavailableonthe CoverDesign:KlausWandeltand Internetat<http://dnb.d-nb.de>. Grafik-DesignSchulz ©2020Wiley-VCHVerlagGmbH&Co. KGaA,Boschstr.12,69469Weinheim, Germany Allrightsreserved(includingthoseof translationintootherlanguages).Nopart ofthisbookmaybereproducedinany form–byphotoprinting,microfilm,or anyothermeans–nortransmittedor translatedintoamachinelanguage withoutwrittenpermissionfromthe publishers.Registerednames,trademarks, etc.usedinthisbook,evenwhennot specificallymarkedassuch,arenottobe consideredunprotectedbylaw. PrintISBN:978-3-527-41159-7 Typesetting SPiGlobal,Chennai,India PrintingandBinding Printedonacid-freepaper 10 9 8 7 6 5 4 3 2 1 V Contents Volume8 AbouttheEditor XI Preface XIII ListofAbbreviations XVII 56 TheoryofSolid/ElectrolyteInterfaces 471 AxelGroß 56.1 Introduction 471 56.2 StructureofElectrochemicalInterfaces 473 56.3 ContinuumModelsofSolid/ElectrolyteInterfaces 479 56.4 AtomisticFirst-PrinciplesDescriptionofSolid/WaterInterfaces 480 56.5 ExplicitConsiderationofVaryingElectrodePotentials 493 56.6 Solid/ElectrolyteInterfacesforNonaqueousElectrolytes 508 56.7 Conclusions 511 References 512 57 Metal–ElectrolyteInterfaces:AnAtomicView 517 MarekNowickiandKlausWandelt 57.1 Introduction 517 57.1.1 ElectrochemicalDoubleLayer 518 57.1.1.1 StructureofMetalSurfaces 518 57.1.1.2 PropertiesofElectrolytes 522 57.1.1.3 Adsorption–Desorption 524 57.1.1.4 HelmholtzModel 525 57.1.1.5 Gouy–ChapmanModel 525 57.1.1.6 Gouy–Chapman–Stern–GrahameModel 526 57.2 ExperimentalMethodsandProcedures 527 57.2.1 Electrochemical“SurfaceScienceApproach” 527 57.2.2 Voltammetry:PrincipleandExperimentalSetups 528 57.2.3 InSituScanningTunnelingMicroscopy 534 57.2.3.1 PrincipleofElectronTunneling 535 57.2.3.2 TunnelingThroughanElectrolyte 537 VI Contents 57.2.3.3 InstrumentalAspects 537 57.3 AdsorptionofAnions 547 57.3.1 Adsorbate-FreeElectrodeSurfaces 547 57.3.2 AdsorptionofHalideAnions 549 57.3.2.1 Chloride,Bromide–Cu(111) 554 57.3.2.2 Iodide–Cu(111) 565 57.3.2.3 ChlorideandBromide–Cu(100) 567 57.3.2.4 Iodide–Cu(100) 572 57.3.2.5 XRDofChloride,Bromide,andIodideonCu(100) 578 57.3.2.6 Bromide–Cu(110) 583 57.3.2.7 Chloride–Cu(110) 585 57.3.2.8 SurfaceCompoundFormation:CopperIodide 592 57.3.3 AdsorptionofSulfideAnions 599 57.3.3.1 Sulfide–Cu(111) 600 57.3.3.2 Sulfide–Cu(100) 608 57.3.4 AdsorptionofThiocyanateAnions 612 57.3.4.1 Thiocyanate–Cu(111) 613 57.3.4.2 Thiocyanate–Cu(100) 614 57.3.5 AdsorptionofPerchlorateAnions 618 57.3.5.1 Perchlorate–Cu(111) 618 57.3.6 AdsorptionofSulfateAnions 621 57.3.6.1 Sulfate–Cu(111)andCu(100) 621 57.4 AdsorptionofAtomicCations 635 57.4.1 MetalDeposition 635 57.4.1.1 Cadmium–Cu(111)andCu(100) 638 57.4.1.2 Copper–Au(111) 647 57.5 AdsorptionofMolecularCations 660 57.5.1 AdsorptionofPorphyrins 663 57.5.1.1 ElectrochemistryofPorphyrinMolecules 663 57.5.1.2 TMPyP–Cu(111) 664 57.5.1.3 TMPyP–Cu(100) 668 57.5.1.4 TTMAPP–Cu(111)andCu(100) 674 57.5.2 AdsorptionofViologens 677 57.5.2.1 ElectrochemistryofViologenMolecules 679 57.5.2.2 Dialkylviologens–Cu(100) 681 57.5.2.3 Diphenylviologen–Cu(100) 687 57.5.2.4 Dibenzylviologen–Cu(100) 693 57.5.2.5 Dibenzylviologen–Cu(111) 703 57.5.2.6 Dibenzyl-dipyridinium–Cu(100) 708 57.5.3 CoadsorptionofPorphyrinsandViologens 710 57.6 FinalRemark 713 References 713 Contents VII 58 X-raySpectroscopyatElectro-catalyticInterfaces 733 DanielFriebel,HirohitoOgasawara,andAndersNilsson 58.1 Introduction 733 58.2 XANESandEXAFS,andHERFDXAS 736 58.2.1 Introduction 736 58.2.2 Methods 737 58.2.2.1 XASinConventionalTransmissionandFluorescenceDetection Modes 737 58.2.2.2 FluorescenceDetectionUnderGrazingIncidence 737 58.2.2.3 HERFDXAS 740 58.2.3 Examples 741 58.2.3.1 Δ𝜇Technique 742 58.2.3.2 HERFDXASandEXAFSStudiesofWell-DefinedFuelCellModel Catalysts 743 58.2.3.3 HERFDXASandEXAFSStudiesofCoOOHand(Ni,Fe)OOH CatalystsforAlkalineWaterElectrolysis 750 58.3 OperandoElectrochemicalX-rayPhotoelectronSpectroscopy 757 58.3.1 AmbientPressureXPS 758 58.3.2 ElectrochemicalXPS 760 58.3.3 OxygenReductionReactiononPt 762 58.3.4 OxygenEvolutionReactiononPt 765 58.3.5 OxygenEvolutionReactiononIrO 765 2 58.4 Summary 768 References 769 59 FundamentalAspectsofElectrocatalysis 773 MatteoDucaandMarcT.M.Koper 59.1 Introduction 773 59.1.1 TwoHundredYearsofElectrocatalysis 773 59.2 Basics 774 59.2.1 IntroductiontoElectrocatalysisandElectrochemicalKinetics 774 59.2.1.1 MacroscopicApproachandEmpiricalTafelEquation 774 59.2.1.2 ElectrochemicalKinetics:FundamentalLawsandtheButler–Volmer Equation 776 59.2.1.3 BasicElectrochemicalKinetics:FurtherConcepts 778 59.2.1.4 MolecularModelofElectronTransfer:theMarcusModel 779 59.2.2 AdsorptionandElectrocatalysis 781 59.2.2.1 ImportanceofAdsorptioninElectrocatalysis 782 59.2.2.2 ModernComputationalApproachestoChemisorptionand Electrocatalysis 784 59.2.3 Well-DefinedSurfacesandStructureSensitivityin Electrocatalysis 788 59.2.3.1 FromSingle-CrystalElectrodestoShape-SelectiveNanoparticles 792 59.2.3.2 ClassificationofReactions 799 59.2.3.3 SurfaceModifications 801 VIII Contents 59.2.3.4 ControllingtheComposition 805 59.2.4 Surface-andProduct-SensitiveTechniquesCombinedto Electrochemistry 807 59.2.4.1 InfraredSpectroscopy 807 59.2.4.2 ElectrochemicalSurface-EnhancedRamanSpectroscopy (EC-SERS) 809 59.2.4.3 Sum-FrequencyGeneration 810 59.2.4.4 DifferentialorOnlineElectrochemicalMassSpectrometry 810 59.2.4.5 Semi-onlineElectrochemicalLiquidChromatography 810 59.2.4.6 ScanningProbeMicroscopyTechniques 811 59.3 KeyReactionsofElectrocatalysis 812 59.3.1 HydrogenEvolution(HER) 812 59.3.1.1 KineticDescriptionofReactionMechanismsofHER 812 59.3.1.2 ModelingofHER:RationalizingTrendsinActivity 814 59.3.2 ChlorineEvolution(CER) 819 59.3.2.1 AnodeMaterialsforChlorineEvolution:DSA 820 59.3.2.2 FundamentalStudies 821 59.3.3 OxygenReductionReaction(ORR) 825 59.3.3.1 FundamentalConsiderationsonORR 825 59.3.3.2 RationalizationofReactionTrendsandSurfaceSensitivityofORRat Pt 830 59.3.3.3 MaterialsforORR 835 59.3.4 OxygenEvolutionReaction(OER) 836 59.3.4.1 FundamentalConsiderationsonOER 836 59.3.4.2 IntermediatesofOER:Energetics 841 59.3.4.3 MaterialsforOER 844 59.4 OtherReactionsinElectrocatalysis 844 59.4.1 OxidationofSmallOrganicMoleculesforEnergyApplications 844 59.4.1.1 COOxidation 844 59.4.1.2 AlcoholOxidation 848 59.4.2 MultiproductReactions:SelectivityIssues 850 59.4.2.1 NitrateReduction 852 59.4.2.2 CO Reduction 857 2 59.4.3 ElectrocatalysisDrivenbyMacromoleculesandEnzymes:An Overview 863 59.4.3.1 GeneralConcepts 863 59.4.3.2 HERandHOR 868 59.4.3.3 OERandORR 870 59.4.3.4 CO Reduction 873 2 59.5 ChallengesinElectrocatalysis 876 59.5.1 ElectrocatalyticAmmoniaSynthesis 876 59.5.2 ElectrocatalyticTransformationofBiomass 877 59.5.3 AdvancedElectrochemicalOxidationProcesses 879 59.5.4 FinalRemarks 879 ABriefGuidetoCitedReferenceBooksandtheLiterature 882 References 882 Contents IX 60 ComplexityandSelf-OrganizationPhenomena:FromSolid/Gasto Solid/LiquidInterfaces 891 AntoineBonnefontandKatharinaKrischer 60.1 Introduction 891 60.2 BistableKinetics 893 60.2.1 BistableKineticsinCOOxidationUnderUHVConditions 893 60.2.1.1 MechanismofCOOxidationUnderUHVConditions 893 60.2.1.2 BistableRegionandHysteresisinCOOxidation 894 60.2.1.3 MathematicalModelingoftheGas-PhaseCOOxidation 896 60.2.2 BistableKineticsinCOElectrooxidationattheSolid/Liquid Interface 897 60.2.2.1 MechanismofCOElectrooxidationonPtinAqueousSolutions 897 60.2.2.2 BistableBehaviorofCOElectrooxidation 898 60.2.2.3 MathematicalModelofCOElectrooxidation 899 60.2.3 BistableKineticsinH ElectrooxidationattheSolid/Liquid 2 Interface 901 60.2.4 ComparisonofBistableBehaviors 902 60.3 OscillatoryKinetics 903 60.3.1 OscillationsinGas-PhaseCOOxidationKinetics:Experimentsand Modeling 903 60.3.2 OscillationsinCOElectrooxidation 907 60.3.2.1 S-NDROscillator 907 60.3.2.2 OscillationsDuringCOElectrooxidationonPtinthePresenceof Anions 908 60.3.3 Oscillationsin(H)N-NDRSystems 918 60.3.4 ComparisonoftheOscillationMechanisms 919 60.4 SpatiotemporalPatternFormation 921 60.4.1 SpatialPatternFormationinCOOxidationUnderUHV Conditions 922 60.4.1.1 FrontPropagationinBistableCOOxidation 922 60.4.1.2 SpatiotemporalPatternsinOscillatoryCOOxidation 924 60.4.2 PatternFormationinCOBulkElectrooxidation 925 60.4.2.1 ExperimentalMethods 925 60.4.2.2 StationaryDomainsDuringGalvanostaticCOElectrooxidation 927 60.4.2.3 SpatialPatternFormationUnderPotentiostaticControlandMigration Coupling:FormationofTuring-TypePatternsandDissipative Solitons 932 60.4.3 PatternFormationin(H)N-NDRSystems 937 60.4.3.1 PatternFormationInducedbyMigrationCoupling:Transitionto Turbulence 937 60.4.3.2 PatternFormationInducedbyGlobalCoupling 938 60.5 ConclusionsandPerspectives 938 References 941 Index 947 XI AbouttheEditor Klaus Wandelt is currently Professor Emeritus at the University of Bonn, Germany, where he was also Direc- toroftheInstituteofPhysicalandTheoreticalChemistry until2010.HereceivedhisPhDonelectronspectroscopy of alloy surfaces in 1975 in München; spent a postdoc- toralperiodattheIBMResearchLaboratoryinSanJose, California, in 1976/1977; and qualified as a professor in 1981inMünchen.Sincethenhisresearchfocusesonfun- damental aspects of the physics and chemistry of metal surfaces under ultrahigh vacuum conditions and in elec- trolytes,ontheatomicstructureofamorphousmaterials, andmorerecentlyonprocessesatsurfacesofplants.ProfessorWandeltwasvisiting scientistattheUniversityofCaracas,Venezuela;theUniversityofHefei,China;the UniversityofNewcastle,Australia;andtheUniversityofCalifornia,Berkeley,and hewasguestprofessorattheUniversityofMessina,theUniversityofPadua,and theUniversityofRomeTorVergata,Italy;theUniversityofLinzandtheTechnical UniversityofVienna,Austria;andtheUniversityofWroclaw,Poland.Hechairedthe surfacephysicsdivisionsoftheGermanandEuropeanPhysicalSocietyaswellasof theInternationalUnionofVacuumScienceTechniquesandApplications,hasorga- nizednumerousworkshopsandconferences,andwaseditorofjournals,conference proceedings,andbooks.
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