d带中心与配位理论ppt课件.ppt

华山论剑:d-bandcenter理论与配位理论,ReactivityDescriptor,simpleandeffective,d-bandcenter理论,BjrkHammer,JensK.Nrskov,HammerB,MorikawaY,NrskovJK.COchemisorptionatmetalsurfacesandoverlayersJ.Physicalreviewletters,1996,76(12):2141.,吉布斯自由能变,ManIC,SuHY,CalleVallejoF,etal.UniversalityinoxygenevolutionelectrocatalysisonoxidesurfacesJ.ChemCatChem,2011,3(7):1159-1165.,Fig2.StandardfreeenergydiagramfortheOERatzeropotential(U=0),台阶图,ManIC,SuHY,CalleVallejoF,etal.UniversalityinoxygenevolutionelectrocatalysisonoxidesurfacesJ.ChemCatChem,2011,3(7):1159-1165.,Fig3.AdsorptionenergyofHOO*plottedagainsttheadsorptionenergyofHO*.,ManIC,SuHY,CalleVallejoF,etal.UniversalityinoxygenevolutionelectrocatalysisonoxidesurfacesJ.ChemCatChem,2011,3(7):1159-1165.,9,Fig4.trendstowardsoxygenevolutionplottedforperovskites.Theoreticaloverpotentialvstheexperimental,火山图,ManIC,SuHY,CalleVallejoF,etal.UniversalityinoxygenevolutionelectrocatalysisonoxidesurfacesJ.ChemCatChem,2011,3(7):1159-1165.,存在问题,Fig5.DFT-GGAadsorptionenergiesofOandOHonPdandPtskinalloysareplottedasafunctionofthecenterofd-bandprojectedonsurfaceatoms.,theexceptionstothed-bandmodelthediscretenatureofelectronicstatesaformidablecomputationalcost,XinH,LinicS.Communications:Exceptionstothed-bandmodelofchemisorptiononmetalsurfaces:Thedominantroleofrepulsionbetweenadsorbatestatesandmetald-statesJ.2010.,配位理论,HongliangXin,FedericoCalle-Vallejo,Fig6.Adsorptionenergiesof*OHatop,describedbygeneralized(left)andhydrogen-containingspeciesagainstCNandInusual(right)coordinationnumbersofthesitestowhichtheadsorbateisbound.,Forexample:CN=(9/12*6+12/12*3),CalleVallejoF,MartnezJI,GarcaLastraJM,etal.FastpredictionofadsorptionpropertiesforplatinumnanocatalystswithgeneralizedcoordinationnumbersJ.AngewandteChemieInternationalEdition,2014,53(32):8316-8319.,Fig7.TrendsintheadsorptionenergiesofextendedsurfacesasafunctionofCN(left)andd-bandcenter(right).,CalleVallejoF,MartnezJI,GarcaLastraJM,etal.FastpredictionofadsorptionpropertiesforplatinumnanocatalystswithgeneralizedcoordinationnumbersJ.AngewandteChemieInternationalEdition,2014,53(32):8316-8319.,Calle-VallejoF,TymoczkoJ,ColicV,etal.FindingoptimalsurfacesitesonheterogeneouscatalystsbycountingnearestneighborsJ.Science,2015,350(6257):185-189.,Calle-VallejoF,LoffredaD,KoperMTM,etal.IntroducingstructuralsensitivityintoadsorptionenergyscalingrelationsbymeansofcoordinationnumbersJ.Naturechemistry,2015,7(5):403-410.,SlaterJC,KosterGF.SimplifiedLCAOmethodfortheperiodicpotentialproblemJ.PhysicalReview,1954,94(6):1498.,Fig10.COadsorptionenergyasafunctionof(a)thegeneralizedcoordinationnumberCN,and(b)theorbitalwisecoordinationnumberCNs(c)d-bandcenterand(d)thecouplingmatrixelement,MaX,