HZSM5分子上乙烯二聚反应机理的理论分析.docxVIP

H—ZSld一5分子筛上乙烯二聚反应机理的理论研究 摘要 本论文通过理论计算研究了H．ZSM．5分子筛孔道内酸性位上的乙烯二聚反 应。主要致力于这样几个关键问题的研究：(1)烯烃低聚过程中C．C键的形成及 碳链有效增长的机理；(2)分子筛酸性的作用；(3)分子筛骨架及孔道结构对反 应选择性的影响。研究采用40T簇模型模拟位于ZSM．5分子筛孔道交叉处 Br6nsted酸性位，应用量子力学和分子力学结合的ONIOM方法计算。研究考察了 分步反应和协同反应两种机理，并考察了孔道结构对反应的影响。应用自然键轨 道分析探究了氢键吸附和反应过渡态结构的电子性质以及分子轨道特征。 计算结果表明，对于分步反应机理来说，乙烯分子首先通过兀．氢键作用吸附 在分子筛酸性位，然后发生质子化反应并形成乙醇盐中间产物，随后乙醇盐又与 第二个乙烯分子反应，发生C—C键结合而得到表面丁醇盐产物。其中乙烯质子化 反应能垒最高，为速控步骤。对于同步反应机理，两个乙烯分子共同吸附在分子 筛酸性位，然后质子化和分子间C．C键结合同时进行，形成表面丁醇盐产物。该 过程的活化能略低于分步反应过程的速控步骤，这意味着这两个机理之间存在竞 争。自然键轨道分析揭示了醇盐中间体与乙烯发生碳链聚合时经过碳正离子过渡 态。分子筛孔道的禁闭效应对乙烯分子的物理吸附起重要作用，并有利于分步反 应机理的竞争。 关键词：乙烯二聚反应；反应机理；ZSM．5分子筛；Br6nsted酸性位；禁闭作用； 密度泛函理论  H-ZSM一5分子筛上乙烯二聚反应机理的理论研究 Abstract In the present work,the dimerization of ethylene on the Br6nsted acid site in H-ZSM一5 zeolite has been investgated by using theoretical calculations．We mainly focus on the following topics：(1)the mechanisms for C—C bond formation and chain propagation in ethylene oligomerization；(2)the effect of zeolite acid sites；(3)the effect of zeolite framework and pore structure Off reaction selectivity．A 40T cluster model was adopted to mimic the Br6nsted acid site located at the channel intersection of ZSM-5 zeolite．All calculations were carded out by the ONIOM method，one of the widespread QM／MM hybrid methods．Two different reaction mechanisms，stepwise and concerted pathways were examined．The natural bond orbital analysis Was used to explore the electronic properties for兀一hydrogen bonding interaction in adsorption complexes and the molecular orbital features at the transition states． The results indicated that in the stepwise mechanism，ethylene firstly adsorbs on the acid site through 7c—hydrogen bonding and then proceeds protonation to form the ethoxide intermediate；then the intermediate reacts、丽廿l the second ethylene molecule to give the surface butoxide product．In which the ethylene protonation shows the highest energy barrier and is confirmed as the rate-limiting step．In the concerted mechanism，two ethylene molec