简介:TheNi-AlalloycontainingCr,FeadditiveswerepreparedasRaneyNiCatalystbyhighenergymilling.ThesizeandsurfacestateofNi-Alalloypowderwerestudiedbyparticlesizeanalyzerandsanningelectronmicroscopy.theStructurewasanalyzedbyXRDandMoessbauermethods.Theresultsshowedthatafterahigh-energymilling(HEM).theNi-Alalloytransformstoanano-scaleNiAlstructurewithrichAl.Byannealingthealloy,ametastableNi2Al3phasecanbeobtained.
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:在Al2O3(0001)衬底上用MOCDVD方法进行了GaN的外延生长,通过X射线衍射(同步辐射源)研究了GaN和Al2O3(0001)的匹配关系。结果表明,经充分氮化的衬底上,GaN以单一的匹配方式沿[0001]方向生长:在Al2O3(0001)衬底未经氮化或氮化不充分时,不同程度地出现了其它三种绕<11-20>晶带轴倾斜一定角度的匹配位向。指出了GaN/Al2O3(0001)的几种匹配方式的晶体学规律。GaN绕<11-20>晶带轴倾斜的匹配方式是其外延生长过程中降低和Al2O3(0001)的晶格失配、释放界面应变的重要机制之一。
简介:评价了具有不同Ni/(Ni+W)原子比的NiW/γ-Al2O3催化剂加氢脱硫活性,对硫化态催化剂进行了EXAFS表征。结果表明,Ni(Ni+W)原子比为0.23的催化剂表面上WS2颗粒最小,有利于形成Ni-W-S加氢脱硫活性相,其反应活性最高。
简介:LocalstructuresofthemolybdenumsulfidespeciesinthesultidedRh-Mo-K/Al2O3catalystswithvariousrhodiumloadingshavebeeninvestigatedbyXAFS.Fromthefittingresults.theMo-Mocoordinationnumberforthesamplefreeofrhodium(ca.3.7)issimilartothatforthecrystallineMoS2,indicatingthatthesupportedsulfidedmolybdenumspeciesmainlypresentaslargepatechesofMoS2-likeslabs.Fortherhodium-modifiedsamples,however,theamplitudesoftheMo-SandMo-Mocoordinationshellsaresharplyreduced,revealingahighdispersionoftheMoS2-likespeciesinthecatalysts,TheschemeofthemicrostructuresofthesulfidedmolybdenumspeciesstabilizedonthealuminasupportisdiscussedbasedupontheanalysisoftheEXAFSdata.
简介:采用XRD、EXAFS技术研究了不同Pd含量的Pd-Mo-K/Al2O3催化剂结构,并关联其合成低碳混合醇性能。结果表明,在氧化态Mo-K/Al2O3催化剂体系中添加Pd后,“K-Mo”物相晶粒变小,分散度提高,说明钯可能和钾钼物种发生了较强的相互作用。经硫化还原处理后,发生了氧硫交换,钼主要以MoS2物种形式存在,其粒度随着Pd含量的增加而明显减小。尺寸的显著变化可能导致MoS2与载体作用形式的改变,从而影响CO加氢催化反应的性能。在硫化态催化剂中,Pd的添加不仅能提高CO加氢合成醇的收率和选择性,而且有利于改善产物的分布。基于以上结果,认为“K-Mo”作用物种和Pd物种均为合成醇的催化活性组份,它们间的相互协同作用使催化剂性能得到显著改善。
简介:Aseriesofrhodium-modifiedMo-K/Al2O3catalystsampleswaspreparedbyvaryingtherhodiumloadingbetween0and1.0wt%andmaintainingmolybdenumandpotassiumcontentsasconstants.ThestructuresofthesampleswerecharaterizedbytechniquesofXRD.LRS.TPR,XPSandEXAFSandcorrelatedtothecatalyticpropertiesofthesamplesforalcoholsynthesisfromsynthesisgas,Itwasfoundthat.intheoxidicrhodium-modifiedsamples.astronginteractionoftherhodiummodifierwiththesupportedK-Mo-Ospeciesoccurs.Thisinteractionfacilitatesthesulfidationandreductionofthesupportedoxo-molybdenumandleadstoadecreaseinthesizeofthemolybdenumspeciesandstabilizationofthecationicrhodiumspeciesonthesamplesduringsulfidation.Uponsulfidation.Thesulfidedmolybdenumspeciesintherhodium-freesampleismanlypresentaslargepatechesofMoS2-likeslabswiththeirbasalsulfurplanesinteractingwiththesupportsurface.Withthemodiricationofrhodiumtothesamples.ThesupportedMoS2-likespeciesbecomeshighlydispersed.asrevealedbythedecreaseintheaveragesizeofthesulfidedmolybdenumspecies.TheinteractionoftherhodiumspecieswiththemolybdenumsomponentmaycausethebasalplanesoftheMoS2-likespeciestobecomeorientedperpendiculartothesupportsurfaceduetofavorablebondingoftheMoS2edgeplanestothesupportthroughMo-O-Albonds.Incomparisonwiththesulfidedsamplefreeofrhodium.thepropertiesoftherhodium-modifiedsamplesforalcoholsynthesisfromsynthesisgasaremuchimproved.Itmostprobablyresultsfromthesynergicinteractionoftherhodiumwiththemolybdenumspeciesthatgivesrisetotheappearanceofthecatalyticallyactivesurfacesofsites.Theco-existenceofcationicandmetallicrhodiumstabilizedbythisinteractionmayberesponsiblefortheincreasedselectivityfortheformationofC2+alcohols.
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。