Encyclopedia of Interfacial Chemistry: Surface Science and Electrochemistry (Vol 1 - Vol 7) PDF
Preview Encyclopedia of Interfacial Chemistry: Surface Science and Electrochemistry (Vol 1 - Vol 7)
ENCYCLOPEDIA OF INTERFACIAL CHEMISTRY SURFACE SCIENCE AND ELECTROCHEMISTRY This page intentionally left blank ENCYCLOPEDIA OF INTERFACIAL CHEMISTRY SURFACE SCIENCE AND ELECTROCHEMISTRY EDITOR IN CHIEF Klaus Wandelt Institute of Physical and Theoretical Chemistry, University of Bonn, Bonn, Germany; and Institute of Experimental Physics, University of Wroclaw, Wroclaw, Poland VOLUME 1 1.1 EXPERIMENTAL METHODS 1.2 SURFACE SCIENCE UNDER ENVIRONMENTAL CONDITIONS AMSTERDAM BOSTON HEIDELBERG LONDON NEWYORK OXFORD PARIS SANDIEGO SANFRANCISCO SINGAPORE SYDNEY TOKYO Elsevier Radarweg29,POBox211,1000AEAmsterdam,Netherlands TheBoulevard,LangfordLane,Kidlington,OxfordOX51GB,UK 50HampshireStreet,5thFloor,Cambridge,MA02139,USA Copyright(cid:1)2018ElsevierInc.Allrightsreserved Nopartofthispublicationmaybereproducedortransmittedinanyformorbyanymeans,electronicormechanical,includingphoto- copying,recording,oranyinformationstorageandretrievalsystem,withoutpermissioninwritingfromthepublisher.Detailsonhowto seekpermission,furtherinformationaboutthePublisher’spermissionspoliciesandourarrangementswithorganizationssuchasthe CopyrightClearanceCenterandtheCopyrightLicensingAgency,canbefoundatourwebsite:www.elsevier.com/permissions. ThisbookandtheindividualcontributionscontainedinitareprotectedundercopyrightbythePublisher(otherthanasmaybenoted herein). Notices Knowledgeandbestpracticeinthisfieldareconstantlychanging.Asnewresearchandexperiencebroadenourunderstanding,changesin researchmethods,professionalpractices,ormedicaltreatmentmaybecomenecessary. Practitionersandresearchersmayalwaysrelyontheirownexperienceandknowledgeinevaluatingandusinganyinformation,methods, compounds,orexperimentsdescribedherein.Inusingsuchinformationormethodstheyshouldbemindfuloftheirownsafetyandthe safetyofothers,includingpartiesforwhomtheyhaveaprofessionalresponsibility. Tothefullestextentofthelaw,neitherthePublishernortheauthors,contributors,oreditors,assumeanyliabilityforanyinjuryand/or damagetopersonsorpropertyasamatterofproductsliability,negligenceorotherwise,orfromanyuseoroperationofanymethods, products,instructions,orideascontainedinthematerialherein. LibraryofCongressCataloging-in-PublicationData AcatalogrecordforthisbookisavailablefromtheLibraryofCongress BritishLibraryCataloguing-in-PublicationData AcataloguerecordforthisbookisavailablefromtheBritishLibrary ISBN978-0-12-809739-7 Forinformationonallpublicationsvisitourwebsite athttp://store.elsevier.com Publisher:OliverWalter AcquisitionEditor:RachelGerlis ContentProjectManager:FionaPattison Designer:MatthewLimbert PrintedandboundintheUnitedStates EDITORIAL BOARD EDITOR IN CHIEF Klaus Wandelt Instituteof Physicaland Theoretical Chemistry,University of Bonn, Bonn, Germany; and Instituteof Experimental Physics,University of Wroclaw,Wroclaw, Poland SUBJECT EDITORS Conrad Becker Aix-Marseille Université, CNRS, CINaM, Marseille, France Peter Broekmann University of Bern, Bern, Switzerland Victor Climent Instituteof Electrochemistry, University of Alicante, Alicante, Spain Francesco Di Quarto Dipartimento di Ingegneria Civile,Aerospaziale edei Materiali Università di Palermo, Palermo, Italy Juan M Feliu Instituteof Electrochemistry, University of Alicante, Alicante, Spain Ueli Heiz Department of Chemistry, Technical University of Munich, Munich, Germany Kurt W Kolasinski West Chester University, West Chester, PA,USA Markus Lackinger Technische UniversitätMünchen &Deutsches Museum, Munich, Germany Falko P Netzer Karl-Franzens University Graz Institute of Physics,Surfaceand Interface Physics, Graz, Austria Roberto Otero Universidad Autónoma deMadrid andIMDEA Nanoscience,Madrid,Spain Miquel Salmeron MaterialsScience Division of theLawrenceBerkeley National Laboratory; and Materials Science andEngineering Departmentof the University of Californiaat Berkeley,Berkeley, CA, USA v vi Editorial Board Andrew Teplyakov Department of Chemistry andBiochemistry, University of Delaware,Newark, DE, USA Pankaj Vadgama Schoolof Engineering and Materials Science,QueenMary University of London, London, UK Soma Vesztergom Eötvös Loránd University,Budapest, Hungary Klaus Wandelt Instituteof Physicaland Theoretical Chemistry, University of Bonn, Bonn, Germany; and Instituteof Experimental Physics,University of Wroclaw,Wroclaw, Poland PREFACE The motivation for compiling and publishing this encyclopedia on Interfacial Chemistry was to promote the communication between chemists, electrochemists, physicochemists, as well as solid-state and surface physi- cists.Thegrowingdiversificationandspecializationofscienceandresearchmakesmutualunderstandingmore andmoredifficult,andthereforeinterdisciplinarycommunicationimperative.Chemiststakegreatadvantageof heterogeneous catalysts often without knowing their properties and operation on the atomic scale. This knowledge,however,isnecessaryforarationaldesignandoptimizationofthecatalysts’activity,selectivity,and stability. Electrochemists and surface physicists working on a similar problem such as film deposition and growth,justindifferentenvironment,maynotshareknowledgeduetodistinctlydifferent“languages,”suchas “underpotential deposition” and “Franck-van-der-Merwe growth” for a similar phenomenon. And there are known differences between the more “practical” approach of chemists and the more “formal” approach of physicists, including the resultant communication “barriers”. On the other hand, all modern experimental analytical tools are based on physical phenomena, such as interaction of radiation with matter and electron tunneling,andareimplementedbyphysicists.Interfacialchemistry,asanexcellentexampleofinterdisciplinary research, can only profit from an unbiased communication and mutual understanding between the different involveddisciplines. Interfaces are the divides between phases, e.g., solid/gas, solid/liquid, solid/solid, liquid/gas, liquid/liquid, and thus an inherent property of heterogeneous systems. “Heterogeneous” sounds, and actually is, more complex than “homogeneous” and therefore calls for a multidisciplinary approach. To investigate and understand “electrocatalysis,” it is certainly helpful to take into account the experience and knowledge of electrochemists and solid-state and surface physicists, two communities that are not known for a close connection. Thedifferenceinpropertiesoneithersideofthedividehastwoimportantconsequences:(1)interfacesare the locations of gradients that are a driving force for processes and (2) interactions across the interface will obviously also alter the properties in interface-near layers of the adjacent phases. If a solid iron surface is exposedtooxygengas,thesurfacewilloxidize;theresultantoxidelayerdiffersfromthepureironunderneath.If twodifferentsolids(orliquids)formacommonphaseboundary,interdiffusionwillchangethecompositionof theinterface-nearregionsonbothsides.Ifaplatinumelectrodeinsulfuricacidsolutionisnegativelypolarized, protons(hydroniumcations)areattractedwiththeconsequencethatthepHnearthePt/electrolyteinterfaceis lower than in the bulk of the solution. And if a copper electrode in hydrochloric acid solution is positively polarized,chlorideanionswillbeattracted,adsorb,andrestructurethesurfacebeforesurfaceatomsformsoluble copperchloride species. Interestingly, not only the presence of interactions across an interface causes alterations on either side, but alsothesuddenabsenceofinteractionsacrossaninterfacehasadecisiveinfluence:Whileanatominthebulkof a solid in equilibrium is surrounded by and interacts with atoms on all sides, an atom at the very surface in vacuumhasnoneighborstointeractwithonthevacuumside.Thisunbalancedrivesthesystemtowardanew equilibriumandcausesarepositioningofthesurfaceatoms;mostintuitivelythesurfaceatoms“relax”toward the bulk of the solid. But there are even cases where the surface atom layer as a whole assumes a two- dimensional lattice structuredifferent from that ofaparallel plane inthe bulk, the surface “reconstructs.” Duetothemissingneighbors,the“unsaturatedbonds”ofsurfaceatoms(incontactwithvacuum)addtothe totalenergyofthesolid.Thesurface“relaxation”and“reconstruction”arearesponseofthesystemtolowerthis “excess surface energy.” The very same argument explains why in equilibrium also the surface composition of multicomponentmaterials,e.g.,alloys,solutions,mustbeexpectedtobedifferentfromthebulkcomposition. vii viii Preface Inequilibriumthesurfacewillbeenrichedwiththoseatomswhoseunsaturatedbondsaddleasttotheexcess surfaceenergy. Sinceitistheverysurfaceofasolid(orliquid),whichfirstinteractswiththeadjacentphase(gas,liquid,or solid),itschemicalcompositionandstructuremustbeknownindetail,i.e.,ontheatomicscale,tounderstand and describe its involvementin chemical processes. Thisinformationisnowadaysavailablethankstothedevelopmentofabroadarsenalofincrediblysensitive high-resolution microscopic and spectroscopic techniques and the so-called “surface science approach.” This approachstartswithstructurallyandchemicallywell-definedsurfaces,e.g.,single-crystalsurfaces,whichunder ultrahigh vacuum conditions are exposed to gases or vapors in a very controlled manner. In this way it is nowadayspossiblenotonlytocharacterizebareandadsorbatecoveredsurfacesandmonitorchangesatom-by- atom but also to modify surfaces by arbitrary manipulation of individual atoms. These achievements and abilities have occasionally misled “insiders” to statements such as “surface science has reached completion.” Apart fromthefact thatclaims likethisinsciencehaveoften beenrash,thereare atleasttwoexpectationson “surfacescience”still.Thefirstis,duetotheubiquityanduniversalimportanceofinterfaces,todisseminatethe knowledge about their fundamental peculiarities more widely to “outsiders” in other disciplinesdbeyond materials sciencesdand in particular to include it more regularly into curricula. The second is to transfer and applytheconceptsandmethods,largelyresultingfromthe“surfacescienceapproach”underultrahighvacuum conditions, to more complex systems in realistic environment such as ambient gases and liquids, as they are dealt with by electro- and bioelectrochemists, materials scientists, and chemical engineers. This transfer, of course, requires to overcome the “barriers” indicated above and, sometimes, may also require the revision of “establishedviews.” The present encyclopedia is an attempt to contribute to this transfer by including publications from rather different but inherently interface-related research fields under the common heading “Interfacial Chemistry.” When I first proposed this project, I suggested 11 subjects: (1) model studies in heterogeneous catalysis, (2) surfacescienceunderenvironmentalconditions,(3)ultrathinfilms,(4)clustersandnanoparticlesatsurfaces, (5)molecularself-assemblyatsurfaces,(6)surface-confinedpolymerization,(7)functionalizationandgrafting of surfaces and nanoparticles, (8) ultrafast surface dynamics, (9) general interfacial electrochemistry, (10) interfacialelectrocatalysis,(11)modelstudiesoncorrosion,andlefta12thsubjectdeliberatelyopenforfurther suggestions.Thereports of19 (!)internationalreviewersofthisproposalwereunisonpositiveandledtothe suggestion of including (12) bioelectrochemistry as the 12th subject. All 12 topics are well covered in this encyclopediathankstotheteamofexcellentsubjecteditorswhomIaskedandwhoagreedtojointhisproject. To accentuate “Interfacial Chemistry” as the common ground, all contributions are explicitly linked by cross- references between papers in the various sections, anddeven though partly very different and subject specificdthe most importantexperimentalmethods are grouped inone separate section “side-by-side.” In addition to the printed version of this encyclopedia, all articles appear within the section “Interfacial Chemistry” of the overarching and well-structured electronic-only Reference Module “Chemistry, Molecular Sciences and Chemical Engineering”1, which supports both an easy accessibility and, thereby, a wide dissemi- nation amongits readership. The coming together of the relevant disciplines is a “steady” process. In 1995 I already edited jointly with S.Trasatti,Milano,aspecialissue“SurfaceScienceandElectrochemistry”ofthejournalSurfaceScience2.Twenty yearslaterin2015IrepeatedthisinitiativetogetherwithA.Gross,Ulm,inSurfaceScience3,andwecametothe “disenchantinginsight”thattheprogressinbringingsolidstatesurfacephysicistsandelectrochemiststogether “wasonlymoderate”andthiseventhoughthe“interestinprocessesatelectrochemicalinterfacesinthecontext of electrochemical energy conversion and storage plays an enormously important role for future energy technology.” As stated above,this encyclopedia is afurtherattempt topromote the mutualinsight inthe importanceof a close collaboration between the involved disciplines, and the electronic version of this encyclopedia embeddedinthesection“InterfacialChemistry”ofthegeneralReferenceModule“Chemistry,MolecularSciences and Chemical Engineering”even offers the possibility of acontinuous updating. Iamdeeplyindebtedtoallthosewhohavecontributedtothiswork,primarily,ofcourse,allauthorsofthe articles,myfellowcoeditorswhoidentifiedandmotivatedtheauthors,andlastbutnotleasttheElsevierstaffat the Oxford office,UK,who organized and handled the workflow. KlausWandelt Editor in Chief Preface ix References 1. ReferenceModuleinChemistry,MolecularSciencesandChemicalEngineering,EditorinChief,J.Reedijk. 2. Trasatti,S.;Wandelt,K.SurfaceScienceandElectrochemistry.Surf.Sci.1995,335,1–447. 3. Gross,A.;Wandelt,K.SurfaceScienceandElectrochemistry-20YearsLater2015,631,1–300.
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