摘要
采用B3LYP/6-31G*水平计算来研究酸性沸石上苯与乙烯的烷基化反应历程,从生成能和反应活化能角度分析并讨论了苯与乙烯的反应机理.选取4T簇模型模拟分子筛的酸性位,使用密度泛函理论对烷基化反应三种不同的反应机理(两个联合反应机理和一个分步反应机理)进行计算分析.结果表明,在联合反应机理中,乙烯的质子化和苯与乙烯间C-C键的形成同时发生;分步反应机理中,首先形成一个稳定的乙醇盐中间物种,然后与苯分子反应形成乙苯.联合机理速控步骤的活化能约为160kJ/mol,分步机理速控步骤的活化能为190.24kJ/mol,因此,酸性沸石上苯与乙烯烷基化反应机理主要以联合机理为主,但分步机理与其有一定程度的竞争。
The acid zeolite catalyzed alkylation of benzene with ethene is investigated at the B3LYP/6-31G level of calculation with a 4T-cluster representing the Brφnsted acid site of the zeolite. The reaction mechanism has been analyzed according to the formation energy and reac- tion activation energy. Three different reaction mechanisms of alkylation, two concerted mech- anism and one stepwise mechanism, have been analyzed by density functional theory. The re- sults showed that ethene protonation and C--C bond formation occur simultaneously in the concerted mechanism. The stepwise mechanism starts with the formation of a stable ethoxide intermediate which subsequently reacts with benzene to form the reaction product. The activa- tion energy for the concerted mechanism was about 160 kJ/mol, while it was 190.24 kJ/mol for the stepwise mechanism. The results showed that alkylation of benzene with ethylene occurred through both concerted mechanism and stepwise mechanism, and they were competitive to each other.
出处
《化学研究》
CAS
2013年第2期189-194,198,共7页
Chemical Research
基金
国家自然科学基金青年基金资助项目(21106073)