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简介:AseriesofoxideizedCO-K-Mo/γ-Al2O3catalystsamples,preparedbyimpregnatingoxidizedK-Mo/γ-Al2O3sampleswithanaqueoussolutionofcalculatedCo(NO3)2andthencalcininginairattemperaturesof350℃,500℃65℃and800℃respectively,weresulfidedandtheninvestigatedfortheactivityinthesynthesisofmixedalcoholsfromCOhydrogenationunderconditionsofp=5.0MPa,T=350℃andGHSV=4800h^-1.TheresultsdemonstratethattheadditionofcobaltpromoterisfavorabletotheformationofhigheralcoholsandtheopimumcalcinationtemperaturesafterimpregnatingwithCo^2+areabout500-650℃.ThestructureofCoandMospeciesontheoxidizedandsulfidedsampleswasdeterminedbyX-raydiffraction(XRD),laserRamanspectrum(LRS)andextendedX-rayabsorptionfinestructure(EXAFS).Foroxidizedsamplecalcinedat350℃,cobaltexistsasCo3O4spectiesandcoversthesurfaceofK-Mo-Ospecies,thestructureofK-Mo-OspeciesisthesameasthatinK-Mo/Al2O3sample.TheinteractionbetweencobaltandK-Mo-Ospeciesisrelativelyweak.Aftersulfidation.Cobaltexistsassulfidecrystalliteswithanoctahedralcoordinatedstructure,andmolybdenumasMoS2crystallites.Foroxidizedsamplescalcinedat500-650℃,CocomponentinteractswiththeK-Mo-Ospeciesanddestroysthelong-rangeorderoftheK-Mo-Ospectesgradually,Aftersulfidation.CotendstoexistasasulfidewithtetrahedralcoordinatedstructureandMostillasMoS2crystallites.Foroxidizedsamplecalcinedat800℃,CocomponentexistsmainlyasCoAl2O4species,mostofwhichcannotbesultidedduringsulfidation.
简介:Amethodbasedupontheweightedtotalcrosssection(WTCS)theoryisproposedtocalculatethephoto-ionisationcrosssectionsandtheradiativerecombinationratecoefficientsbetweenthefundamentallevelofCOandthemainelectronicstatesofitscorrespondingion.Totalphoto-ionisationcrosssectionsandradiativerecombinationratecoefficientsaredeterminedfromthecalculationofelementaryvibrationalphoto-ionisationcrosssections.TransitionsbetweenCO~+(X,AandB)andCO(X)areconsidered.Totalphoto-ionisationcrosssectionsandrecombinationcoefficientsarecomputedinthetemperatureinterval500-15000K.
简介:采用X-射线吸收近边结构(XANES)和扩展X-射线吸收精细结构(EXAFS)技术,对用不同原料盐和不同焙烧温度制得的Co/γ-Al2O3催化剂中钴的微观结构进行了详细的表征。XANES结果表明,以硝酸盐为原料盐于500℃焙烧的样品Co(N)-500,其Co-K边的近边结构与标样Co3O4相似,而其它样的近边结构则与标样CoAl2O4相似。随焙烧温度提高。在吸收边前的弱吸收峰(1s→3d)逐渐增强。在吸收阈值处,主吸收峰(1s→4p)的分裂变得更明显,950℃焙烧的样品,在主吸收峰上升过程中出现了肩峰(1s→4s)。这些特征表明,样品中钴主要以Co^2+离子形式存在。钴离子与载体作用的加强,使非化学计量的尖晶石相在结构上与化学计量的CoAl2O4越来越接近。EXAFS结果表明,样品Co(N)-500中,钴主要以Co3O4的形式存在。其第一配位壳层Co-O配位数明显低于标样Co3O4,说明该相具有较高的分散性。其它所有样品中,钴主要以非化学计量的尖晶石相存在,其第一配位壳层Co-O配位数随焙烧温度从500℃提高到950℃,与标样CoAl2O4越来越接近;相同焙烧温度下,从醋酸钴制得的Co(A)系列样品更容易形成Co-Al尖晶石相。XANES和EXAFS结果很好地说明了前文中样品对CO氧化和乙烯选择还原NO反应的活性规律。
简介:Anodesusedfordirectmethanolfuelcells(DMFCs)werefabricatedbymagnetronsputteringprocess.Ahouse-madeplasmasputteringsystemwasusedtodepositPtandPtRuontoun-catalyzedgasdiffusionlayers(GDLs)atdifferentradiofrequency(RF)powersandsputteringgaspressures.ThethinfilmcatalystlayerswerecharacterizedbyX-raydiffraction,energydispersiveX-rayanalysis,andX-rayphotoelectronspectroscopy.Thesputteredanodeswereassembledincustom-mademembraneelectrodeassemblies(MEAs)withacommercialcathodeandtheelectricalperformanceofthesinglecellweretestedunderpassivemethanolsupply,ambienttemperatureandair-breathingconditions.TheelectrochemicalperformanceoftheanodespreparedwithPtRualloywascomparedwithareferenceanodesputteredwithPtonly.X-raydiffractionandX-rayphotoelectronspectroscopyrevealedthatplatinumandrutheniumexistedasaformofalloy.ThecellpolarizationmeasurementsshowedthatallthePtRualloycatalystshadbetterelectrochemicalperformancethanthePt_1catalyst,andthePt_(0.43)Ru_(0.57)catalystachievedthebestperformance.