Surface and interface science. Volume 8: Interfacial Electrochemistry

505 Pages·2012·25.596 MB·English

by  Klaus Wandelt

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)
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Volume6:Solid-GasInterfacesII
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Volume7:LiquidandBiologicalInterfaces
Volume8:InterfacialElectrochemistry
PrintISBN978-3-527-41159-7
oBookISBN978-3-527-68059-7(Volume7)
oBookISBN978-3-527-68060-3(Volume8)
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Volume10:ApplicationsofSurfaceScienceII
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oBookISBN978-3-527-82249-2(Volume9)
oBookISBN978-3-527-82250-8(Volume10)
EditedbyKlausWandelt
Surface and Interface Science
Volume8:InterfacialElectrochemistry
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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.