Hydrogen Adsorption on Au-Supported Pt and Pd Nanoislands A Computational Study of Hydrogen Coverage E ff ects - Santana, Mel - 2021 -

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pubs.acs.org/JPCCArticleHydrogenAdsorptiononAu-SupportedPtandPdNanoislands:AComputationalStudyofHydrogenCoverageEffectsJuanA.Santana*andJoshuaMeléndez-RiveraCiteThis:J.Phys.Chem.C2021,125,5110−5115ReadOnlineACCESSMetrics&MoreArticleRecommendations*sıSupportingInformationABSTRACT:WehavestudiedthedissociativeadsorptionofhydrogenunderhighcoverageconditionsofadsorbedhydrogenonPdandPtnanoislandssupportedonAu(111)usingdensityfunctionaltheorycalculations.TheresultsrevealthatforPd/Au(111),thefreeenergyofhydrogenadsorptionΔGiscloseto0kJ/molwhenthecoverageofadsorbedhydrogenisnear1ML,wheretheavailablecatalyticsitesarelocatedattheedgesofthePdnanoislands.InthecaseofPt/Au(111),ΔG≈0kJ/molunderabroadrangeofhydrogencoverageconditions,from1to3ML,dependingonthesizeofthePtnanoislands.ThisisthecasebecausetheavailablecatalyticsitesarelocatedatboththestepsandterracesofPtnanoislands.ThesefindingsindicatethatAusurfaceswithPdorPtnanoislandsoffercatalyticsiteswithΔG≈0forhydrogenreactions,onekeyfactorforanidealelectrocatalystforhydrogenreactions.101.INTRODUCTIONboundaryandtheinnerregionofthePtnanoislands.Liaoand12ThedevelopmentandoptimizationofactiveanddurableYaupreparedPtnanoislandswithdifferentphasesonAu(111)nanostructuredsurfacecatalystsrelyheavilyonourunder-andfoundthattheactivitytowardHERwasuniqueineachstandingofhowparticlesize,sitecoordination,andsubstratephase,suggestingtheexistenceofmultipletypesofadsorptioneffectsmodulatecatalyticproperties.1−7Thehydrogensites.TheseresultsshowthattheinterfaceformedinAu-oxidation/evolutionreactions(HOR/HER)havebeenexten-supportedmetalnanoparticlesiscomplex,andtheinterpretationsivelyexploredtostudytheeffectsofparticlesize,activesiteofexperimentalfindingsrequiresrealisticatomic-levelmodelscoordination,andsubstrateeffectsonPtandPdnanoparticlessubstantiatedbyaccuratecalculations.8−27Inthisregard,variousdensityfunctionaltheory(DFT)supportedonAu(111).ThereactivitytowardHOR/HERincreasesconsiderablywhenAu(111)withsub-monolayercalculationshavebeenperformedtostudytheadsorptionof8,9,17,18,37,19,26,388,9,17coveragesofPtorPdisemployedasanelectrocatalystinsteadhydrogenonPdandPtnanoislandsofthecorrespondingPdandPtsurfacesortheiroverlayersonsupportedonAu(111).Theresultsofthesecalculationsreveal11−16,20−25,27Au.Thesupportedelectrocatalystsaretwo-dimen-thattherearemultiplestableadsorptionsitesforhydrogenonsional(2D)nanoparticles(nanoislands)withdiametersof2−30PdandPtnanoislandonAu(111)underthelow-coverage11−16,20,22−24,27nm.Asimilarlyenhancedelectrocatalyticactivityconditionofadsorbedhydrogen.TheidentifiedadsorptionsitesDownloadedviaUNIVOFPRINCEEDWARDISLANDonMay16,2021at14:49:21(UTC).Seehttps://pubs.acs.org/sharingguidelinesforoptionsonhowtolegitimatelysharepublishedarticles.forHERhasbeenreportedfornanoislandsofRhonAuandPdincludethehollowsites(hydrogenis3-foldcoordinated),thesurfacesaswellasforbimetallicnanoislandsofPdRhonAuandbridgesite(hydrogenis2-foldcoordinated),andthesitesatthe28,29,11,30Ptsurfaces.Au-supportedmetalnanoislandsareusefulPt/AuandPd/Auboundaries(rimsites).8,9,17−19,26,38However,model-systemsnotonlyforHOR/HERbutalsoformanyotheronekeyfactorforanidealHOR/HERelectrocatalystsistohave31catalyticprocesses,includingC−Cbondsplitting,methanol,3233afreeenergyofhydrogenadsorptionnearzero,ΔG(θHads)≈andformicacidoxidation,andelectro-oxidationofCO.37,39−43Au-supportedmetalnanoislandsexperiencesize-dependent0.ΔG(θHads)isafunctionofthecoverageofadsorbedcompressivestressduetofinite-sizeeffects,16,19,33−35resultingin37,39−43hydrogenθH.Furthermore,experimentalandcomputa-adstheformationofsupportednanoislandsthatarenotalignedwithtionalresultsindicatethatHOR/HERatlowoverpotentialonPt12thesubstrate.Asaresult,Au-supportedmetalnanoislandscanelectrodes,forinstance,takeplaceunderhighcoveragehaveabroaderrangeofadsorptionsitesthanregular9,17−19,2610surfaces.TheworksofLiangetal.andLiaoandYa12showsuchabroadrangeofadsorptionsites.Liangetal.10Received:December29,2020usedtheelectrochemicalscanningtunnelingmicroscope(n-Revised:February16,2021ECSTM)36techniqueandshowedthatthecatalyticactivityforPublished:March1,2021HERismaximalatthePd/AuboundaryonPdnanoislandson10Au(111).Ontheotherhand,PtnanoislandsonAu(111)displayedcatalyticactivityratheruniformlyacrossthePt/Au©2021AmericanChemicalSocietyhttps://dx.doi.org/10.1021/acs.jpcc.0c115665110J.Phys.Chem.C2021,125,5110−5115

1TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticle39,40,44−48conditionofspectatoradsorbedhydrogen.Therefore,molecule,andthemetalslab,respectively.ThenumberoftheactivesitesforHOR/HERonPtandPdnanoislandsadsorbedhydrogenatomsisnH.ThenumberofsurfacemetalsupportedonAu(111)arelikelymetalsiteswithpreadsorbedatomsisN,andθHads=nH/Nisthecoverageofadsorbedhydrogenatoms.hydrogen.ForhydrogenadsorbedonPtnandPdnsupportedonInthepresentwork,westudythedissociativeadsorptionofAu(111),thehydrogencoverageθHisevaluatedastheratiomolecularhydrogenunderhighcoverageconditionsofadsorbedadshydrogenonPtandPdnanoislandssupportedonAu(111).ThenH/n,wheren=7,19,31,or61.ThedifferentialhydrogenadsorptionenergywascalculatedassystemsofPtnandPdn(n=7,19,37,and61)supportedonAu(111)areemployedasmodelsofmetal−supportednano-NΔE()θH=[−−EnNEnint(/)int((1)/)N]sizedmetalislands.ThesemodelscanbringinsightintomultipleadsΔn(2)aspectsofHOR/HERonPtandPdnanoislandssupportedonAu(111),including(i)thechangeinΔGwiththehydrogenFinally,thefreeenergyofadsorptionΔG(θHads)isapproximatedcoverageθH,(ii)thechangeinΔGwithparticlesize,and(iii)asadswhetherornottherecouldbemetalsiteswithΔG(θH)≈0onadsΔ≈GE()θθHHΔ+()ZΔPE−TΔSadsadsPtandPdnanoislandssupportedonAu(111).Moreover,these−1systemsarereasonablemodelsofadsorptionsitesonterraces,=ΔE()2θH+3kJmol(3)adsedges,corners,andkinksofmetal-supportedmetalnanoislands.whereΔZPEandTΔSarethedifferenceinzero-pointenergyandentropy,respectively,betweenadsorbedhydrogenand2.METHODSmolecularhydrogeninthegasphase.AsshowninpreviousDFTcalculationswerecarriedoutemployingtheViennaAb-calculations,42,43formostmetalsurfacesΔZPEand−TΔS49−51initioSimulationPackage(VASP).ThePerdew−Burke−correctionsforthedissociative-adsorptionofHaddupto522Ernzerhof(PBE)variantofthegeneralizedgradientapproximately23kJmol−1perHat300K.Weapproximateadsapproximation(GGA)wasusedtorepresentexchange-thefreeenergybyadding23kJmol−1tothedifferentialcorrelationeffects.Theioniccoresweredescribedbytheadsorptionenergy.ThecalculatedbondenergyofH2is−436kJ53,54projectoraugmented-wave(PAW)method.Theelectronicmol−1and−408kJmol−1afterZPEcorrection.one-particlewavefunctionswereexpandedonaplane-wavebasissetuptoanenergycutoffof350eV.Thetechniqueof3.RESULTSANDDISCUSSIONfractionaloccupationnumbers,withalevelwidthof0.05eVwasTostudytheeffectsofthecoverageofadsorbedhydrogenontheused.AlltotalenergieswereextrapolatedtokbT=0eV.ThedissociativeadsorptionofmolecularhydrogenonPtandPdinteractionbetweentherepeatedslabswasmodifiedforadipolenanoislandssupportedonAu(111),akeystepistoidentifythecorrectionasimplementedinVASP.Werestrictedourlow-energyconfigurationsofsystemscomprisedofmultiplecalculationstothespin-averagedstrategybecausethehydrogenatomsadsorbedonthemetalnanoislands.Thereareadsorptionenergiesofhydrogenevaluatedfromspin-polarized−1multipleavailablemethodologiestoautonomouslyfindlow-andspin-averagedcalculationsdifferonlyby1kJmol.58−61energyconfigurationsofchemicalsystems.However,Theeffectsofthecoverageofadsorbedhydrogenonthehydrogenatomsareabsorbedonwell-definedmetalsurfacedissociativeadsorptionofmolecularhydrogenwerestudiedonsitesonPt(orPd)onAu(111),andlow-energyconfigurationsPtnandPdn(n=7,19,31,and61)supportedonAu(111).Forcanbeestimatedwithstandardoptimizationmethods.Wecomparison,calculationswerealsoperformedforthehydrogenexploredmultipleconfigurationsofhydrogenadsorbedonPtnadsorptiononPdandPtoverlayersonAu(111)surfaces.TheandPdn(n=7,19,31,and61)nanoislandsdepositedonPtnandPdn(n=7,19,31,and61)modelsweresimulatedwithAu(111).However,wefocusourdiscussiononthelow-energy(4×4),(6×6),(8×8),and(10×10)surfacesmodelsoffourconfigurationsandprovideresultsforalltheconfigurationsthatatomiclayers,separatedbyavacuumregionover10Å.DuringwereexploredinTablesS1−S5andFiguresS1−S7inthegeometryoptimization,thetwo“bottom”atomiclayersoftheSupportingInformation.surfacemodelswerekeptfixedatthecalculatedlattice55Figure1ashowsΔG(θH)forthedissociativeadsorptionofconstants,whiletheremainingatomswereallowedtorelaxadsuntilallresidualforceswerelessthan0.02eV/Å.ForhydrogenonPt19andPd19supportedAu(111)asestimatedwithgeometricaloptimization,Brillouinzoneintegrationswereeq3.Figure1b−kshowsthestructureofadsorbedhydrogenoncarriedoutwith(5×5×1),(3×3×1),and(1×1×1)k-thenanoislands.Therearevariousobservationsworthpointsampling56forthe(4×4),(6×6),andthelargersurfacementioning.First,Pt19andPd19onAu(111)showdifferentcells,respectively.Weusedafinermeshofk-pointstocalculateΔG(θHads)profiles.However,forbothmetals,ΔG(θHads)showsenergeticandelectronicproperties:(7×7×1),(5×5×1),andsomefluctuationbecausehydrogenatomsfirstsaturatethelow-(3×3×1)forthe(4×4),(6×6),andthelargersurfacecells,energysites,andasthesesitesareoccupied,themoreenergeticrespectively.vacantsitesbecomefeasible.AtlowhydrogencoveragesθH

2TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticlemol.TheresultsforΔG(θH)≈0kJ/molindicatethattheadsactivesiteonPt19/Aucanbethehollowsitesontheterrace(Figure1c,e)andalsothesitesatthePt/Auboundary(Figure1d,f).Ontheotherhand,onlythesitesatthePd/AuboundaryhaveΔG(θHads)≈0kJ/molforPd19/Au(Figure1h,i).Thecoverageofadsorbedhydrogenattheequilibriumpotential(θ0)),whereΔG(θ)≈0,isakeyparametertounderstandHadsHads37,39theHOR/HERonmetalsurfaceandmetalnanoparticles.Thevalueofθ0isalsoanimportantquantitytohelpidentifyHads40,41,70thenatureoftheactivesiteforHOR/HER.Thefindings10inFigure1areinlinewiththeworkofLiangetal.showingthatthecatalyticactivityforHERismaximalatthePd/AuboundaryinPdnanoislandsonAu(111)butuniformacrosstheinnerandedgeregionsofPtnanoislandsonAu(111).Now,weturntoexaminenanoislandssmallerorlargerthanPt19andPd19onAu(111).Figure1.(a)FreeenergyofadsorptionΔGadsasafunctionofhydrogencoverageonPt19andPd19onAu(111).Thelowerpanelsshowthestructureof0.63,0.79,1.26,1.74,and2.05MLofadsorbedhydrogenatomson(b−f)Pt19and(g−k)Pd19.Theredcirclesonpanelsb−kindicatethehydrogenadsorptionsitesthatarebeingfilledattheindicatehydrogencoverage.NumericalvaluesforΔGadsareprovidedinTableS2oftheSupportingInformation.ofhydrogenwithlowcoordination,themetal-HbondderivesfromtheinteractionofH-sanddorbitalsofthemetal,64whichisFigure2.FreeenergyofadsorptionΔGadsasafunctionofhydrogencoverageon(a)Ptnand(b)Pdn(n=19and61)onAu(111).Resultsratherinsensitivetothestabilizationofsorbitalsinthemetal.arealsoincludedforoneoverlayer(1ML)ofPtandPdonAu(111).Therefore,hydrogenpreferslowcoordinationonPtbuthigh17NumericalvaluesareprovidedinTablesS2−S5oftheSupportingcoordinationofPd.Inotherwords,theedgesversusterracesInformation.locationpreferenceofhydrogenonPtandPdmainlycomesfromtheopenshell5d96s1electronicconfigurationofPtandclosed-shell4d105s0electronicconfigurationofPd.Figure2displaysΔG(θ)forPtandPd(n=19and61)onHadsnnThesecondobservationinFigure1aisthatΔG(θHads)Au(111)andPtandPdoverlayersonAu(111).ThegeneralincreasesforbothPt19andPd19onAu(111)untilreachingbehaviordescribedaboveofΔG(θHads)forPt19andPd19onvaluescloseto0kJ/molathydrogencoveragesθH≈1ML.AtAu(111)isalsoobservedfortheothernanoislands;resultsforadshighervaluesofθHads,ΔG(θHads)forPd19continuestoincreasePtnandPdn(n=7and37)onAu(111)areprovidedinFigureS9oftheSupportingInformation.AkeyfindingfromcomparingbutthatofPt19fluctuatesaroundΔG(θHads)≈0untilθHads≈2.1ΔG(θHads)forPtnandPdnonAu(111)isthatthehydrogenML.NotethatforPd19/Au,themaximumpossibleθHads≈1MLcoverageθHadswhereΔG(θHads)≈0changeswiththesizeofthebecauseathighercoverage,ΔG(θH)>0kJ/mol,andtheadsPtnanoislandsbutremainbasicallyconstantforPd.Sucheffectadsorbedhydrogenintermediateswillnotbestableat300K.comesfromhydrogenlocatingpreferentiallyontheedgesofPtTheseresultsshowthatPd19reachedfullsaturationatlowernanoislands.ThenumberofedgesitesdecreaseswithincreasinghydrogencoveragesthanPt19.Indeed,Ptclustershavebeenparticlesize,resultingintheobservedsizedependencyofθshowntohaveamuchhigherhydrogenadsorptioncapacitythanHads65−67whereΔG(θH)≈0forPtbutnotforPd.InthecaseofPtandPd.ThehigherhydrogencapacityofPtcanbeexplainedbyadsthefactthathydrogenpreferslowcoordinationonPtbuthighPdoverlayersonAu(111)surfaces,ΔG(θH)isverysimilarforadscoordinationofPd.Also,therepulsiveinteractionsbetweenthebothsystems.Aspreviouslyreported,39,46,47,57,71thehydrogenadsorbedhydrogenatomsareexpectedtobelargerforPd19/Auatomsarepreferentiallyadsorbedonhollowsitesupto1MLonbecausethechargethatistransferredtoadsorbedhydrogenisbothPtandPdoverlayersonAu(111).ΔG(θH)increaseswithadshigherfromPdthanPtclusters;seeFigureS8oftheSupporting68,69increasingθHduetotherepulsiveinteractionsbetweenInformationforaBadertypechargeanalysis,whereaclearads72distinctioncanbeobservedforthechargetransferredfromPdadsorbedhydrogenatoms.Afterallthehollowsitesare39,46,47,57,71andPttotheadsorbedhydrogenatomsasexpectedfromtheiroccupied,hydrogenadsorbsonthetopsites.differentworkfunction(5.70eVforPtvs5.23eVforPd).55ΔG(θH)≈0isreachedatcoveragesθHcloseto1MLonadsadsAthirdandfinalobservationinFigure1aregardsthelocationbothPtandPdoverlayersonAu(111)surfaces.However,theofactivesitesonPt19/AuandPd19/AuwhenΔG(θHads)≈0kJ/overlayeredsurfacesdonotshowadsorptionsiteswith5112https://dx.doi.org/10.1021/acs.jpcc.0c11566J.Phys.Chem.C2021,125,5110−5115

3TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleΔG(θHads)≈0,insharpcontrastwithPtnandPdnnanoislandshydrogendissociativeenergyontheAu(111)surface.ThevalueofΔG(H@Au)dependsonthesizeofthenanoislandsandissupportedonAu(111).ThepresentresultscanhelpexplainthelargeronAusitesthatarenearthenanoislands,butitisover30kJmol−1;seeTablesS2andS3inSupportingInformationandobservedincreaseincatalyticactivityatlowsubmonolayer1721,22,25ourpreviousworkfordetails.Therefore,thisvalueshouldbecoveragesofPdandPtonAu(111).PdandPtclosetothelowestlimitforEdiffbecauseadsorbedhydrogenwillnanoislandsonAu(111)haveidealcatalyticsitesforhydrogennotbestablewhenΔG(θH)>0kJ/mol.Ourestimatedadsreactions,i.e.,hydrogenadsorptionsiteswithΔG(θH)≈0.energiesforhydrogenspilloverfromPtorPdnanoislandstoadswell-definedAu(111)surfacesshowthatsuchaprocessisnotthermodynamicallyfavorableevenunderhighcoverageconditionsofadsorbedhydrogen.TheevolutionofH2willtakeplacebeforehydrogenspilloverstotheAu(111)surface.Thisresultreflectsthelowreactivityofwell-definedAu(111)surfacestowardthehydrogenadsorption.Thecasecouldbe13differentforPtandPdnanoislandsoverdefectedAusurfacesandAusurfaceswithembeddedPtorPdatoms(alloyedsurfaces),whichcouldhavemoreactiveAusites.4.CONCLUSIONSDFTcalculationswereperformedtostudythedissociativeFigure3.Averagenearest-neighbordistanceasafunctionofhydrogenadsorptionofmolecularhydrogenunderhighcoveragecoverageon(a)Ptnand(b)Pdn(n=19,31,and61)onAu(111).TheconditionsofadsorbedhydrogenonPtnandPdn(n=7,19,errorbarsindicatethestandarddeviationofthedistances.Numerical31,and61)supportedonAu(111).ThesemetalnanoislandsvaluesareprovidedinTablesS2−S4oftheSupportingInformation.representmodelsoftheadsorptionsitespresentunderlowcoverageconditionsofPdandPtonAu(111)aswellasadsorptionsitesatthecornerandkinkdefectsinextendedFigure3displaystheaverage⟨Pt−Pt⟩and⟨Pd−Pd⟩nearest-overlayeredAusurfaces.TheresultsofthecalculationsshowneighbordistanceasafunctionofhydrogencoverageθH.ForadsthatthefreeenergyofhydrogenadsorptionΔG(θH)dependsadsbothmetals,theaveragemetaldistancesincreasewithhydrogenstronglyonthehydrogencoverageonPdandPtnanoislandsoncoverageasexpectedfromthebondorderconservationAu(111).Therefore,computationalidentificationofcatalyticprinciple.TheaveragemetaldistancesalsoshowfluctuationsiteswithΔG(θH)≈0onthesesurfacesrequiresthewithhydrogencoveragebecauseofthechangeinthehydrogenadssimulationofhighcoverageconditionsofadsorbedhydrogen.absorptionsite.UponsaturationofmostPdnanoislandswithhydrogenatoms,wherecoveragesθHads≈1ML,the⟨Pd−Pd⟩InthecasesofPtnandPdnsupportedonAu(111),theresultsshowthatthereareadsorptionsiteswithΔG(θH)≈00anddistancesincreasetovaluescloseto2.9Å.TheonlyexceptionisadsthatthesesitesaredifferentonPdandPt.ForPdnanoislands,Pd7/Au,wherethe⟨Pd−Pd⟩distancesreachvaluescloseto2.82Å;resultsforPt7/AuandPd7/AuareprovidedinFigureS10ofvaluesofΔG(θHads)≈00werefoundforhydrogenadsorbedontheSupportingInformation.InthecaseofPtnanoislands,thethePd/Auboundary.ForPtnanoislands,thereareadsorption⟨Pd−Pd⟩distancesincreasetovaluescloseto2.85ÅuponsiteswithΔG(θH)≈0bothatthePt/Auboundarybutalsoonadssaturationwithhydrogenatoms.EstimatesofsuchchangesintheterracesitesofthePtnanoislands.Thepresenceofsiteswith⟨Pt−Pt⟩and⟨Pd−Pd⟩withhydrogencoverageθHadscouldbeΔG(θH)≈0canhelpexplainthereportedincreasedcatalyticadsusefulforthecharacterizationofAu-supportedPdandPtactivityoflowsub-monolayercoverageofbothPdandPton12nanoislandsunderelectrochemicalconditions.Au(111).ThedifferentactivesitesonPdandPthelptoOnefinalaspectthatcanbeexploredwithourmodelsofPtrationalizethefactthatcatalyticactivityforHERonPdandPdnanoislandssupportedonAu(111)isthepossibilityofnanoislandsonAu(111)isobservedmainlyonthePd/AuthespilloverofatomichydrogenfromtheactivemetaltotheAuboundary.13,20,27substrate.Hydrogenspilloverhasbeenobservedandstudiedonsystemscompriseofaregular(111)metalsurfacewithembeddedPdatoms.73Therefore,hydrogenspillovercould■ASSOCIATEDCONTENT*sıSupportingInformationbeenhancingthecatalyticactivityofmetal-supportedmetalcatalystsatsub-monolayercoverages.Yet,weexploredtheTheSupportingInformationisavailablefreeofchargeathydrogenspilloveronsmallPtandPdclustersonAu(111).17https://pubs.acs.org/doi/10.1021/acs.jpcc.0c11566.Theenergyforthemigration(diffusionenergy,Ediff)ofFiguresandtableswithnumericalvaluesofthecalculatedhydrogenatoms(hydrogenspillover)fromPt3andPd3tothepropertiesofhydrogenadsorbedonPtnandPdn(n=7,Au(111)surfacewascalculatedat80kJmol−1and38kJmol−1,19,37,and61)nanoislandssupportedonAu(111)17respectively.Suchresultssuggestthatthespilloverof(PDF)hydrogenplaysnoneorverylittleroleinthecatalysisofhydrogenonPtandPdnanoislandsonAu(111).Thatcalculated17diffusionenergiescorrespondtolow-coverageconditionsof■AUTHORINFORMATIONadsorbedhydrogen,wheretherearenotrepulsionsbetweenCorrespondingAuthoradsorbedH.However,thediffusionenergycanbeapproximatedJuanA.Santana−DepartmentofChemistry,UniversityofasEdiff≈ΔG(H@Au)−ΔG(θHads),whereΔG(H@Au)isthePuertoRicoatCayey,Cayey,PuertoRico00737,United5113https://dx.doi.org/10.1021/acs.jpcc.0c11566J.Phys.Chem.C2021,125,5110−5115

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