应用理论计算研究MCM-分子筛相邻酸性位上乙烯和苯的吸附.docVIP

应用理论计算研究MCM-22分子筛相邻酸性位上乙烯和苯的吸附 第29卷第4期 Vol29No.4 催化 ChineseJournalofCatalysis 2008年4月 April2008 文章编号:0253—9837(2008应用理论计算研究MCM.22分子筛相邻 酸性位上乙烯和苯的吸附 倪丹,周丹红,张佳 (辽宁师范大学化学化工学院功能材料化学研究所,辽宁大连116029) 研究论文:366～372 摘要:应用ONIOM计算方法研究了MCM一22分子筛超笼12元环上存在两个酸性位时的酸强度及其与骨架铝之间距离的关 系,并研究_r乙烯和苯分子吸附的规律.计算采用52T簇模型和B3LYP/6—31G/MND0方法.结果表明,存在两个酸性位 且两个骨架铝之间间隔1个骨架硅时,酸强度比孤立的酸性位明显降低;当间隔的硅原子数增加时,酸强度呈上升趋势,间隔 3个以上骨架硅时,其酸强度与孤立的酸性位几乎没有差别.对于乙烯的吸附,当两个骨架铝之间问隔1～4个骨架硅时,其 吸附能几乎没有差别(31～35kJ/mo1);对于苯的吸附,当两个骨架铝之间间隔1个骨架硅时,其吸附能有所提高,因为两个桥 羟基同时对苯分子产生氢键吸附作用当两个骨架铝之间的距离增大时,苯的吸附能几乎相同(21～29kJ/mo1)若两个乙烯 分子或苯分子同时吸附在双酸性位上,其吸附能与单个分子在孤立酸性位吸附时几乎没有差别.应用自然键轨道计算分析了 吸附配合物的电子结构,进一步探明了乙烯和苯在分子筛酸性位上吸附的本质. 关键词:密度泛函;MCM22分子筛;乙烯;苯;吸附能 中图分类号:0643文献标识码:A StudyofEthyleneandBenzeneAdsorptiononBr6nstedAcidSites inMCM.22ZeolitesbyTheoreticalCalculation NIDan,ZHOUDanhong,ZHANGJia (InstituteofChemistryJorFunctionalizedMaterials,CollegeofChemistryandCkemicalEngineering LiaoningNormalUniversity,Dalian16029,Liaoning,China) Abstract:TheONIOMmethodwasusedtoperformthecomputationalstudyontheacidstrengthofdoubleacid sitesinthe12member—ringofMCM一22zeolite.ThecalculationwascarriedoutbytheB3IYP/6—31G/MN— DOmethodbasedonthe52Tclustermode1.rFhedependencyoftheacidstrengthontheintervaldistanceofthe frameworkAlatomswasexamined.andtheadsorptionofethyleneandbenzeneontheadjacentacidsiteswasin— vestigated.Thecalculationresultsindicatedthatwhentwoacidsitesexistedneareachotherandspacedoutby oneSiatom,theaciditydescendsobviouslywithrespecttotheisolatedacidsite.IftheSiatomnumberbetween twoframeworkAlatomsincreases.theacidityrisesup.WhentheSiatomnumberismorethanthree.theacid strengthreachesasteadyvalue,beingequivalenttolheisolatedsystem.ForC2H4adsorption,itsadsorptionen— ergyinallcasesis31—35kJ/mo1.independentontheintervaldistancebetweentheframeworkAlatoms.For C6H6benzeneadsorption,itsadsorptionenergyonnextnearestneighbouracidsitesishigherthanthatonsingle acidsite,andwhentheSiatomnumberismorethanthree,itsadsorptionenergyis21—29kJ/mo1.Theadsorp— tionenergyo