简介:采用程序升温氮化的方法制备了钼氮化物催化剂,并用EXAFS方法研究了氮化前后Mo原子的局域配位情况。负载MoO3样品的径向结构函数中有三个峰其中前两个峰对应着最近的Mo-O配位壳层,但是第一个峰与第二个峰的比例比晶体MoO3中的比例大很多,表明分子筛负载的MoO3具有更紧密的结构。氮化以后,Mo2N样品的径向结构函数中有三个峰,对应于一个Mo-N和两个Mo-Mo配位壳层,与面心立方模型符合的很好。根据X射线衍射和EXAFS谱的计算表明,Mo2N中的N原子使Mo-Mo键拉长并削弱。分子筛负载的Mo2N样品具有与非负载Mo2N样品相似的径向结构函数,只是对应于Mo-N壳层的峰较弱,表明负载的MoO3更难氮化。
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: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:采用溶胶-凝胶法制备CoMoO4催化剂,经K助化后分别在空气中于400-800℃下进行焙烧,得到氧化态样品,然后经硫化制得硫化态K-Co-Mo催化剂,对氧化态样品的乙醇分解性能及硫化态样品的CO加氢合成低碳醇的反应性能进行了测试,运用X射线衍射(XRD)和扩展X光吸收精细结构(EXAFS)对样品进行结构表征,乙醇分解性能测试表明,催化剂的表面酸性较弱,且随着焙烧温度的升高变化不大,合成醇性能测试结果则显示,催化剂的焙烧温度升高后,其合成醇的产率逐步降低,但醇选择性基本不变,经400℃焙烧的样品,具有最好的催化活性。结构分析结果表明,氧化态样品中存在多种K-Mo-O物种,且随着焙烧温度的提高,钾铝之间作用增强,样品更难以被完全硫化。
简介:InthedischargeofEASTtokamak,itisobservedthat(2,1)neoclassicaltearingmode(NTM)istriggeredbymodecouplingwitha(1,1)internalmode.Usingsingularvaluedecomposition(SVD)methodforsoftX-rayemissionandforelectroncyclotronemission(ECE),thecouplingspatialstructuresandcouplingprocessbetweenthesetwomodesareanalyzedindetail.TheresultsofSVDforECErevealthatthephasedifferencebetweenthesetwomodesequalstozero.Thisisconsistentwiththeperfectcouplingcondition.Finally,performingstatisticalanalysisofγ1/1,ζ1/1andω2/1,wefindthatγ1/1moreaccuratelyrepresentsthecouplingstrengththanζ1/1,andγ1/1isalsostronglyrelatedtothe(2,1)NTMtriggering,whereγ1/1isthewidthof(1,1)internalmode,ζ1/1istheperturbedamplitudeof(1,1)internalmode,andω2/1denotesthemagneticislandwidthof(2,1)NTM.