Interfacial electrochemistry: theory, experiment, and applications

961 Pages·1999·55.93 MB·English

by  Andrzej Więckowski

INTERFACIAL
ELECTROCHEMISTRY
Theory, Experiment, and Applications
edited by
ANDRZEJ WIECKOWSKI
University of Illinois at Urbana-Champaign
Urbana, Illinois
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Foreword
Thediscoveryoftheinterrelationofelectricityandchemicalchangegoesbacktothebeginningofthenineteenthcentury,
andthatcenturysawgreatphenomenologicaladvancessuchasthepreparationofnewelementsbyDavy,theinvention
ofpowersourcesbyPlana~andGrove,andgreatindustrialprocessessuchastheelectrochemicalsmeltingofaluminum
byHallandHeroult. Faradaymadeakeyadvanceintheunderstandingofelectrochemicalprocessesthroughhisquan
titativelawsofelectrolysis,andGibbsshowedhowthermodynamicscouldbeappliedtoequilibriumcellsandtoobtain
thecompositionofinterfaces. However,thestudyofthekineticsofelectrodereactionsdidnotbeginuntilTafel's obser
vations at the beginning ofthe twentieth century. Progress in understanding the rate ofelectrode reactions was slow
despitetheworkofButler,Volmer,Frumkin,andHeyrovsk)'.Evenin1947theoverpotentialwasbeinginterpretedbysome
atthe LiverpoolFaradayDiscussioninthermodynamictermsorasaresultofblockagebyasurfacefilm. Nevertheless,
theworkofFrumkinandhiscolleagues,followedbythatofRandles,ledtotheintegrationofelectrochemicalkineticsinto
the generalscheme ofthe kinetics ofinterfacial reactions, butwiththe special feature ofrate constants dependenton
potential.Theinvestigationofthe compositionandstructureofthe metal-electrolyte interphasewas moredeveloped,
largelybecauseofthepropertiesofmercury, inthepioneeringworkofGouy.These developmentsledtotheuse ofthe
droppingmercuryelectrodebyHeyrovsk)'andalmostthe onlyworkonacleanelectrodesurfaceinthefirsthalfofthe
century.The precision measurement ofthe interfacial capacityby Grahame followed. Despite the great advances in
techniques,until1970measurementsweremacroscopicandtheinterpretationsinevitablymadecontactwithexperimen
tation at this level, even though optical interrogation ofthe interface was already being discussed in the Faraday
Symposiumofl970inLondon.
Thegreatadvanceofthelastthreedecadesofthetwentiethcenturyhasbeentheintroductionofmolecularleveltech
niques thatenabledtheinterpretationofelectrochemicalphenomenaatthislevel.Thelandmarkherewasthemeeting
in Snowmass, Colorado in 1979 on non-conventional approaches to the studyofthe solid-electrolyte interface (T. E.
Furtak, K. L. Kliewer, andD.W Lynch,eds., SurfaceScience101 (1980)). Althoughearlierattemptstousevibrational
spectroscopy were made, the breakthrough came in the workofFleischmann, Hendra, and McQuillan, followed by
Van Duyne, on surface-enhanced Ramanspectroscopyand thatofBewickand Robinson, who showedhow infrared
spectroscopycouldbeusedtostudythemetal-electrolyteinterface.Almostatthesametime,Hubbardandhiscolleagues
showedhowan electrode couldbe transferredcleanlyinto anultrahighvacuumwhere the structure and composition
ofitssurfacecouldbeexaminedusingthepanoplyofelectronspectroscopiesandscatteringtechniquesdevelopedbyvac
uumsurfacescientists.BythefollowingdecadeClavilierhadadvancedtheknowledgeofsingle-crystalelectrodesurface
byasimpleandelegantmethod, andthediscoveryofscanningtunnelingmicroscopybyBinnigandRohrerhadledto
thestudyofsurfacestructureinsitu.Theseexperimentaladvanceswereparalleledbygreatertheoreticalinsightmade
possiblebytheenormouslyincreasedpowerofdigitalcomputers,whichenabledmodelsatthemolecularleveltobecom
paredwithdirectobservations. Itmustbe saidthatthesophisticatedtheoryofelectrodekinetics awaitsacomparable
verificationatthemolecularlevel, althoughthestochastic approachdiscussedby Fleischmannetal. atthe Snowmass
meetingseemstopointtheway.
iii
iv Foreword
Thisvolumepresentsaccountsofmanyoftheoutstandingdevelopmentsofthepasttwodecades,bythescientistsfrom
variousdisciplineswhohavebeenattractedtothestudyofelectrochemicalinterfacesbythepossibilityofmakingsignifi
cantprogress in understanding this importanttype ofsystem.Their namesguaranteethegreat interestofthe articles,
whichreflectthecurrentstateofknowledgeofelectrochemistyatthemolecularlevel.Thesechaptersprovideafirmbasis
forthosewhowishtocontinueinnovationinthisfieldinthecomingcentury.Theywillnodoubtacknowledgetheirdebt
to Andrzej Wieckowski for his foresight and skill in assembling this overview ofthe many aspects of interfacial
electrochemistry.
RogerParsons
DepartmentofChemistry
The University
Southampton, England
I
I,
I
~
L-
l
Preface
Weofferthereaderanauthoritativetreatisethatprovidescomprehensivecoverageofrecentadvancesininterfacialelec
trochemistryby prominentscholars in thefieldand depicts itsprospectsfor growth.Thevolume will be ofinterestto
electrochemists,surfacescientists,andtheorists,aswellastomaterialsscientistsandengineerswhovaluetheelectrified
solid-liquidinterfaceasareactivezoneformaterialsprotection,modifications,andtransformations.Thisisamodern
reference for instruction in electrochemistry, electroanalysis, and surface science on the graduate level that offers a
perspectiveonthesize,content,andgrowthdynamicsofinterfacialelectrochemistry,attheturnofthecentury.
Therecognitiongiventoelectrochemistrybytheinternationalscientificcommunityinthesecondhalfofthetwentieth
centuryhasbeenhigh duetobothitsfundamental andappliedcontributions,withtwoNobelPrizehighlights: in1959
to HeyrovskY for polarography and in 1992 to Marcus for theory of electron transfer, including heterogeneous
(electrochemical) electron transfer reactions. The recent period of development has focused predominantly on
characterizationproperties ofthesolid-liquidinterfaceand hasgiven riseto interfacialelectrochemistryas a rapidly
expandingdiscipline. Research inthisfieldisidentifiedbyprogressintheoryandmodelinginsupportofexperiments,
continuingprogress in the understandingofcharge transfer reactions, investigations ofthe effectofelectrode surface
structure on interfacial reactivity (structure-function relationships) and remarkable expansion of the array of
electrochemical, thermodynamic, and physical methods used to further the understanding ofthe interface on the
molecularlevel.
Althoughinterfacialelectrochemistryismainlyanexperimentalarea,theoryandmodelingareacrucialadjunct,and
applications are derived from the fundamental experimental findings.Therefore, in orderto demonstrate the overlap
amongtheory, experiment,andapplications, thetheoreticalchaptersarepresentedfirst, followedbythekeyresultsfor
basicexperimentalstrategiesfromwhichapplicationprospectsemanate.Theapplicationsdiscussionsarenotmeantto
bereviewsofcurrentelectrochemicaltechnologies, buttodescribeexperimentalstrategiesthathaveclearlyidentifiable
applied goals or contexts. Although the division is more intuitive than formal, the reader should be able to navigate
throughthevolumeeasily,andseetheprevailinglogicinthetheory---+ experiment---+ applicationsequence.
A newapproach, comprehensivelyreviewedin thisvolume, hasbasicallyalignedelectrochemists'interestsin inter
faceswiththemainstreamofmoderntopicsinsurfacescienceandphysicalchemistry[1, 2].Theprimarydevelopment
hasbeenthedemonstrationoftheintimateconnectionbetweenelectrochemicalexperimentandpracticeofinterfacial
spectroscopies,bothexsitu[3]andinsitu[4-6],suchas:(i)electronspectroscopiesofultrahighvacuum(UHV)surface
science [3, 7-9], including double-layer modeling in UHV [10], (ii) optical techniques in the visible range:
electro-reflectance[7],secondharmonicgeneration[11,12]andRamanspectroscopy(mainly,surfaceenhancedRaman
spectroscopy)[13],(iii)infraredspectroscopyandrelatedarea[5,6],(iv)synchrotronx-raytechniques[4,14],(v)scanning
probe microscopies: scanning tunneling microscopy (STM) and atomic force microscopy [15], includingjoint STM
and UHV efforts [16], and, even more recently, (vi) solid-state nuclear magnetic resonance (NMR) [17]. The
electrochemistry-spectroscopyconnectionisamplyhighlightedinthevolume(see, for instance,chaptersbySoriaga,
v
vi Preface
Weaver,Tadjeddine, Pettinger, and their collaborators).There has been a parallel refinement in conventional electro
chemical and thermodynamic [18] methods (chapters by Lipkowski et al. and by Silva and Martins), as well as
progressinelectrochemicalinstrumentation,includingtheavailabilityoffullycomputerizedpotentiostatsandfacilitated
datastorage,processing,anddisplay,andastrongdrivetouseotherphysicaltechniquesinthefield: radioactivelabeling
[19], quartz microbalance [20], and mass spectrometry [21]. Recent success in these strategies is well documented in
the book. The attractiveness and future prospects ofthe field have encouraged a healthy influx ofnumerous young
researchers, and the field continues to expand rapidly. Because of the complex nature of solid-liquid electrified
interfaces, theoretical investigationshavelongusedsimplifiedmodels, suchas continuumdielectricandchargedwall
models, todescribethesolutionandmetalcomponentsoftheinterface[22]. Morerecently, however, MonteCarloand
moleculardynamics simulations, and density functional theorydirectdynamics (ultimately, quantum mechanical ab
initio)treatmentshaveprogressedtothelevelwhereitisnowpossibletomodelthemolecularstructureoftheelectrolyte
neardiscreteandchargedmetal surfaces, aswellas topredictelectrostaticparameters suchaswork function changes
andspectroscopicfindings [23,24].Thoroughdiscussions ofthesetopicsareprovidedinPart I,Theoryand Modeling
byHaley, Blum,Berkowitz,Rikvold,Sellers,Anderson,Newton, Ulstrup,andbytheircollaborators.
The book aspires to cover recent progress of interfacial electrochemistry on the molecular level, requiring
crystallographicallywell-definedelectrodesofknownelementalsurfacecompositionastemplatesforadsorption,and/or
electroderearrangementprocesses.Thechaptersonsurfacereconstruction(seethechapterbyKolb) andmodelingof
electrical double-layer in ultrahigh vacuum (Ito et al. and Pirug et al.) manifest this trend most accurately. Such
well-definedelectrodesare preparednotonlyviaultrahighvacuumproceduresderivedfrom surface science, butbya
simple and ingenious so-called flame-annealing method [25]. In the chapter by Clavilier, the originator of the
flame-annealing method, a strongcaseis made about thevirtues ofhis technique andfor prospectsfor itscontinued
utilization. Althoughthecontributionbyexsitutechniquestoelectrochemistryandelectrocatalysisremainsstrong(see
chaptersbyHubbard,Wandelt,Soriaga,Tanaka,andtheircollaborators),thesimplicityoftheflame-annealingapproach
hasopenedthefieldtomanyinvestigatorswho,mostprobably,wouldnotconsiderusingpreparativemethodsrequiring
extensiveuseofvacuuminstrumentation.Ithasalsopavedthewayfornewapproachestoaccessthestructureofelectrical
double-layer, for instance, reliable measurements ofpotentials ofzero charge using forced desorption-replacement
reactions(see the chapterbyFeliuetal.). Besides, theflame-annealing methodsaresimpletocouplewithin situ tech
niquesofelectrodesurfacecharacterization.Theumbrellasubfieldofelectrochemistrycoveringelectrochemicalresearch
withsuchwell-characterizedsystemcanbetermedelectrochemicalsurfacescience.Theprogressinelectrochemicalsur
facescience,includingtheutilizationofincreasinglyrefinedelectrochemical,physicalandtheoretical(see,forinstance,
Blum and Huckaby et al. in Ref. 23) methods, has immensely improved our understanding ofmolecular and ionic
adsorption,ultrathinmetallicfilmformation,andelectrocrystallizationprocessesandhasallowedinvestigatorstodem
onstratestructure-function relationshipsinelectrochemistryfor thefirsttimesincerateprocessesbecamethesubject
ofelectrochemicalscrutiny.ThissubfieldofinterfacialelectrochemistryiscomprehensivelydocumentedinPartII,Elec
trochemicalSurfaceScience.
The purpose ofthis book is to document that interfacial electrochemistry is a dynamic discipline with a rapidly
expandingscientificprofile. Along thisline, Conwayand Savadogo, depictcurrenttrends inelectrochemicalhydrogen
science[26].ChaptersbyBernasek,Marcus,Jerkiewicz,andcollaboratorsdemonstratetheadvancedeffortsinpromot
ingcorrosion research(alsosurfaceoxidation, dissolution, andpassivationprocesses[27])tobecomeavibrantpartof
contemporaryphysicalandmaterialsscienceactivity. InPartIII,NonmetallicandSemiconductorElectrodes,Kulesza
etal. review themostrecentprogressandopportunitiesin solid-stateelectrochemistry, andMcCreeryetal. reporton
thecurrentstatusofelectrochemistryofcarbonelectrodes[28]. Further,thestatusoforganicandinorganicsurfactants
(thinfilms) onsolidelectrodesurfacesishighlightedinchaptersbyLipkowski,Buess-Herman,andtheircollaborators,
and the cutting-edgehighlights related to semiconductor/solarenergy [29] and to conducting polymer research [30],
are provided in chapters by Schultze, Augustynski, Uosaki, Rajeshwar, Stickney et al., and by Mark and Rubinson,
respectively. The reader will find very useful the updated demonstration of such powerful techniques as infrared
spectroelectrochemistry(chaptersbyWeaver,Korzeniewski,andIwasitaandcollaborators),synchrotronx-raymethods
(chapter by Ocko/Adzic et al.), scanning tunneling microscopy (chapters by Kolb, Itaya, and collaborators), sum fre
quencygeneration(Tadjeddineetal.),SERS(Weaveretal.),differentialelectrochemicalmassspectrometry(Baltruschat),
radiotracers (Honlnyi), electroactive integrated optical waveguide spectroelectrochemistry (Armstrong), quartz
microbalance (Hepel), and UHV (e.g.,Wieckowski et al.). Likewise, the topics covered in Part IV, Electrocatalysis
(beginning with the chapterbyTrasattithat dealswith catalysis on conductive oxides), conclusivelydemonstrate that
-
Preface vii
interfacialelectrochemistryis an importantpartofthe globaleffortto develop cleanand renewable energy resources,
including fuel cells (see, for instance, chapters by Stuve, Ross/Markovic, Hamnett, Lamy, McBreen, and their
collaborators).
Thus,thiscollectionof51chaptersservesasafocalpointforthepresentationofthediverserangeoftopicsininterfacial
electrochemistry, both experimental and conceptual, with regard to their future impact in physical surface sciences,
analyticalchemistry,andenergy-basedtechnologies.Wehopethatthiscompilationofchaptersreflectingviewpointsby
manyleadingexpertsonsolid-liquidinterfacialissueshasproducedthematerialoflastingvaluetoelectrochemistry.
Fromamorepersonalperspective,thisvolumewasdevelopedasaforumtooffertheauthorsanopportunitytosum
marizerecentcontributionsthattheybelievearemostgermanetotheirspecificresearchareasandfuturework.Wehope
thattheyhaveenjoyedpreparingtheircontributionsandweareconfidentthatreaderswillrecognizethissentiment.Most
ofthe chapters are not formal reviews, since presenting such reviews would amount to replicating the mission of
prominentmonographsinelectrochemicalscience.Therefore,thereadershouldnotexpectthatallauthorshavecovered
a comprehensive range oftopics relevant to their interests. As a supplement, a snapshotofrecently published books,
chapters, and proceedings volumes in the interfacial electrochemistry area is added, to provide supplementary and,
perhaps, unifYingmaterialfor thescopeofworkcoveredinthisvolume, seeReferences.
THEFUTURE
Electrochemists have championed the use ofmodern surface spectroscopic and theoretical methods in fundamental,
atomic-level studies, butthe periodoftheir scrutinyhasbeentoobriefto capitalize ontheiraccomplishments.There
aremanychallengesahead. Forinstance:
(i) Thesignificanceofthe electrode surfaceas adynamicentityincontrollingthe structure/reactivityofelectrified
interfacesneedstobevigorouslydemonstratedviabothexperimentalandtheoreticalwork.
(ii) RatesofcatalyticreactionsinvolvingorganicfuelsarestilltoolowtosatisfYthedemandsofthefuelcellcommunity,
andnomorepotentcatalyticmaterialsareinhand.
(iii) Thedegradationofconstructionandelectronicmaterialsisfarfrombeingundersatisfactorycontrol.
(iv) Nanoscaleprocedures[31]emergingfromelectrochemistryarestillintheir infancy.
(v) Theoretical formalisms that fulfill a criterion of predictability as to the structure, binding energies, lateral
interactions,andinterfacialreactivityhavenotyetbeenfullydeveloped.
(vi) Thenatureofthesurfacechemicalbondremainsinadequatelyunderstooddespiteprogressintheidentificationof
surfacestructureandadsorbatebindingsitesforavarietyofsystems.
(vii) Understanding of the dissociative electron transfer is poor as compared with that already developed for
outer-sphereelectrontransferreactions[32].
(viii) Knowledgeofelementarystepsinvolvedinmetaldepositionhasnotyetmeaningfullyaffectedthepraticeofindus
trial deposition methods, and the contribution of interfacial electrochemistry to studies of electrified
.. li~id-liquidandbiologicalinterfacesneedstoberapidlyexpanded.
Aboveall,confrontedwiththeavalancheofexperimentaldataofhighprecisionanddepth,electrochemistsincreasingly
needexpertisefromtheoristsinterestedinthemodelingofsolid-liquidinterfacesusingpowerfulquantummechanical,
moleculardynamics,andMonteCarlotechniques. Electrochemistsalsoneedtopushforfurtherexpansioninresearch
methodology thatwillallowthemtoproducemoreexperimentaldataonthequantummechanicallevel, which, hasso
farbeenrare.
ACKNOWLEDGMENTS
I gratefully acknowledge editorial assistance by my colleagues Professors G. Tremiliosi-Filho and W Chrzanowski.
Ms. Arvilla Humes' invaluable help with the management ofthe volume throughout the editing process is highly
appreciated.
AndrzejWieckowski
viii Preface
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Contents
Foreword RogerParsons iii
Preface v
Contributors xiii
I. TheoryandModeling
1. TheoreticalModelingoftheSolid- LiquidInterface: ChemicallySpecificSimulationMethods
J W Halley, SeanWalbran, andDavidLeePrice
2. TheoryoftheMetal-ElectrolyteInterface 19
L. Blum, MarcD. Legault,andDaleA. Huckaby
3. StructureofWaterattheWater-MetalInterface: MolecularDynamicsComputerSimulations 33
M. L. Berkowitz, In-Chul Yeh, andEckhardSpohr
4. MonteCarloMethodsforEquilibriumandNonequilibriumProblemsinInterfacialElectrochemistry 47
G. Brown, P A. Rikvold, S. J Mitchell, andM. A. Novotny
5. ElectronicStructureCalculationsofPolyatomicOxyanionsAdsorbedonMetalSurfaces 63
PatriciaParedesOlivera, MartinPatrito, andHarrellSellers
6. Quantum Chemical Modeling of Electrocatalytic Reactions, Including Potential Dependence: Beginning
Stages 83
AlfredB. Anderson
7. Theory and Computational Modeling: Medium Reorganization and Donor-Acceptor Coupling in Electron
TransferProcesses 97
MarshallD. Newton, S.WFeldberg, andJ F Smalley
8. InterfacialElectronTransferinElectrochemistryandInSituScanningTunnelingMicroscopy 115
EsbenP Friis, MarianneHallbergThuesen, lingdongZhang, andlens Ulstrup
II. ElectrochemicalSurfaceScience
9. ElectrochemicalProcessesInvolvingHAdsorbedatMetalElectrodeSurfaces 131
BrianE. Conway
ix
x Contents
10. ReconstructionofGoldSurfaces 151
A. S. DakkouriandD. M. Kolb
11. InSituSurfaceX-RayScatteringStudiesofElectrosorption 175
JiaX Wang, RadoslavR. Adiic,and Benjamin M. Ocko
12. Atomic-ScaleAspectsofAnodicDissolutionofMetals: StudiesbyInSituScanningTunnelingMicroscopy 187
KingoItaya
13. AugerSpectroscopyofElectrodeSurfaces 211
ArthurTHubbard
14. Flame-AnnealingandCleaningTechnique 231
Jean Clavilier
IS. InterfacialChemistryofPalladium Electrodes 249
ManuelP Soriaga,Youn-Geun Kim, andJose E. Soto
16. ElectrochemicalDouble-LayerModeling UnderUltrahighVacuumConditions 269
G. PirugandH P Bonzel
17. Modelingofthe Electrochemical Double-Layer in UltrahighVacuum: Adsorption ofSulfuric Acid Species on
Pt(lll) 287
Yoshitaka ShingayaandMasatokiIto
18. AdsorbateBondingandReactivityinElectrochemistry: SomeVibrationalSpectroscopicLinkstoSurfaceScience
andInterfacialChemistry 301
MichaelJ T#averandShouzhongZou
19. SumandDifferenceFrequencyGenerationatElectrodeSurfaces 317
AbderrahmaneTrldjeddineandAlainLeRille
20. VibrationalCouplingEffectsonInfraredSpectraofAdsorbatesonElectrodes 345
CarolKorzeniewski
21. AFourierTransformInfraredSpectroscopyApproachtoDouble-LayerandElectrocatalysisProblems 353
TeresaIwasitaandElenaPastor
22. SecondHarmonicGenerationAnisotropyfrom SingleCrystallineElectrodeSurfaces 373
BrunoPettinger, Christoph Bilger,Jacek Lipkowski, andWolfgangSchmickler
23. AmphiphilicandIonicSurfactantsat ElectrifiedInterfaces 405
Dan Bizzotto,VladZamlynny, Ian Burgess, CraigA. Jeffrey, Hong-QiangLi, John Rubinstein, RodA. Merril, Jacek
Lipkowski, ZbigniewGalus, AndrewNelson, andBrunoPettinger
24. OrderedOrganicAdlayersat ElectrodeSurfaces 427
ClaudineBuess-Herman, SandraBare, MireillePoelman, andMichel Timkrieken
25. CapacitiveandVoltammetricResponsesfromSteppedFacesofGold 449
A. Fernando SilvaandAnaMartins
26. Electrochemistry, Spectroscopy, and Scanning Tunneling Microscopy Images of Small Single-Crystal
Electrodes 463
VCliment, R. Gomez, J M. Orts, A. Rodes, AntonioAldaz,andJuan M. Feliu
27. RadiotracerStudiesofAdsorption/SorptionPhenomenaatElectrodeSurfaces 477
GyorgyHrJr(inyi
28. StructureandReactivityofRhodium andRhodium-BasedAlloys 493
Ken-ichi TanakaandAkiraSasahara
...........