简介:AnAu/ceria(0.44%,massfraction)catalystcontaininggoldionswaspreparedbyamodifieddepositionprecipitationmethod,andtheevolutionofgoldionsinthecatalystanditsinfluenceonthecatalysisofCOoxidationwereinvestigated.Itwasfoundthattheas-preparedcatalystcontaininggoldionswithhighvalencecouldfullyoxidizeCOat–10°CinitiallybutwasdeactivatedgraduallyatlowtemperaturesduringthereactionwithCOortreatmentbyunpurifiedair.ThedeactivationofthecatalystduringCOoxidationortreatmentofitbyunpurifiedairwasindependentandprogressiveatlowtemperatureswhiletheactivityofthecatalystatrelativelyhightemperatureswasmaintainedwell.DuringthereactionwithCOortreatmentbyunpurifiedair,theXPSresultsindicatethatgoldspeciesevolvedfromhighvalencetolowvalenceandthediffusereflectanceUV-Visspectrashowthathighvalencegoldwasreducedtochargedgoldclusters,goldclustersgrewtosmallgoldcrystalsandsmallgoldcrystalsgrewtolargegoldparticles.Accordingly,thehighvalencegoldcorrespondedtotheactivityatlowtemperaturesandthemetallicgoldwasactiveandrelativelystableathightemperatures.Theturnoverfrequencies(TOF)ofthecatalyststreatedbydifferentmethodsat273Kdecreasedwiththeevolutionofgoldspeciesfromhighvalencetolowvalence,nomaximumofTOFwasobservedalthoughgoldparticlesinthecatalystattainedtoabout2―3nmduringthetreatment.AnAu/ceriacatalystwithagoldloadof0.87%(massfraction)maintainedagoodactivityforCOoxidationwithin18hatroomtemperature.Thecatalystswerecharacterizedviatransmittedelectronicmicroscopy(TEM),inductivelycoupledplasmaopticalemissionspectrometry(ICP-OES),X-raydiffraction(XRD)andBETspecificsurfaceareaandUV-VisDRSaswell.
简介:ThreeseriesofCeO2/CuOsampleswerepreparedbyimpregnationmethodandcharacterizedbyXRD,N2adsorption-desorption,temperatureprogrammedreduction(TPR),XPSandTEMtechniques.IncomparisonwiththesamplespreparedwithCuOasinitialsupport,thesampleswithCu(OH)2asinitialsupporthavehigherreducibilitiesandsmallerrelativeTPRpeakareas,andalsolargerspecificsurfaceareasatcalcinationtemperaturesof400℃–600℃.Asaresult,Cu(OH)2isbetterthanCuOasinitialsupportforpreferentialoxidationofCOinexcessH2(CO-PROX).Thebestcatalyticperformancewasachievedonthesamplecalcinedat600℃andwithanatomicratioofCe/Cuat40%.XPSanalysesindicatethatmoreinterfacelinkagesCe-O-Cucouldbeformedwhenitwascalcinedat600℃.AndtheatomicratioofCe/Cuat40%ledtoaproperreducibilityforthesampleasillustratedbytheTPRmeasurements.
简介:ThemorphologyeffectofZr-dopedCeO2wasstudiedintermsoftheiractivitiesintheselectiveoxidationofstyrenetostyreneoxideusingtert-butylhydroperoxideastheoxidant.Inthepresentwork,ZrdopedCeO2nanorodsexhibitedthehighestcatalyticperformance(yieldofstyreneoxideandTOFvalue)followedbynanoparticlesandnanocubes.FortheZr-dopedCeO2nanorods,theapparentactivationenergyis56.3kJ/mol,whichismuchlowerthanthevaluesofcatalystssupportedonnanoparticlesandnanocubes(73.3and93.4kJ/mol).Thehighresolutiontransmissionelectronmicroscopyresultsindicatedthat(100)and(110)crystalplanesarepredominantlyexposedforZr-dopedCeO2nanorodswhile(100)and(111)fornanocubes,(111)fornanoparticles.TheremarkablyincreasedcatalyticactivityoftheZrdopedCeO2nanorodsismainlyattributedtothehigherpercentageofCe3+speciesandmoreoxygenvacancies,whichareassociatedwiththeirexposed(100)and(110)crystalplanes.Furthermore,recyclingstudiesprovedthattheheterogeneousZr-dopedCeO2nanorodsdidnotloseitsinitialhighcatalyticactivityafterfivesuccessiverecycles.
简介:CuO-CeO2catalystswerepreparedbyaureaprecipitationmethodfortheoxidativesteamreformingofethanolatlow-temperature.Thecatalyticperformancewasevaluatedandthecatalystswerecharacterizedbyinductivelycoupledplasmaatomicemissionspectroscopy,X-raydiffraction,temperature-programmedreduction,fieldemissionscanningelectronmicroscopyandthermo-gravimetricanalysis.OverCuOCeO2catalysts,H2withlowCOcontentwasproducedinthewholetestedtemperaturerangeof250–450C.Thenon-noblemetalcatalyst20CuCeshowedhigherH2productionratethan1%Rh/CeO2catalystat300–400Candtheadvantagewasmoreobviousafter20htestingat400C.TheseresultsfurtherconfirmedthatCuO-CeO2catalystsmaybesuitablecandidatesforlowtemperaturehydrogenproductionfromethanol.
简介:HighactiveandstablegoldcatalystssupportedoncrystallineFe2O3andCeO2/Fe2O3werepreparedviathedeposition-precipitationmethod.ThecatalystwithaAuloadof1.0%calcinedat180°CshowedaCOconversionof100%at-8.9°C,whileAu/CeO2/Fe2O3convertedCOcompletelyat-16.1°C.Evenhavingbeencalcinedat500°C,Au/Fe2O3stillexhibitedsignificantcatalyticactivity,achievingfullconversionofCOat61.6°C.ThecatalystwithalowAuloadof0.5%couldconvertCOcompletelyatroomtemperatureandkepttheactivityunchangedforatleast150h.N2adsorption-desorptionmeasurementsshowthatthecrystallinesupportspossessedahighspecificsurfaceareaofabout200m2/g.CharacterizationsofX-raydiffractionandtransmissionelectronmicroscopyindicatethatgoldspecieswerehighlydispersedasnanoorsub-nanoparticlesonthesupports.Evenafterthecatalystwascalcinedat500°C,theAuparticlesremainedinanano-sizeofabout6―10nm.X-rayphotoelectronspectrarevealthatthesupportedAuexistedinmetallicstateAu0.ThemodificationofAu/Fe2O3byCeO2provedtobebeneficialtotheinhibitionofcrystallizationofFe2O3andthestabilizationofgoldparticlesindispersedstate,consequentlypromotingcatalyticactivity.