文献类型：期刊文献

中文题名：单原子Cr、Fe和Ni催化乙炔环三聚反应机理研究

英文题名：DFT Study on the Mechanism of Acetylene Cyclotrimerization Catalyzed by Cr, Fe, and Ni

作者：朱文闻[1,2];刘振[3]

机构：[1]上海石化工业学校,上海201512;[2]江苏大学化学化工学院,江苏镇江212013;[3]华东理工大学化工学院,上海200237

年份：2021

卷号：35

期号：2

起止页码：158

中文期刊名：分子催化

外文期刊名：Journal of Molecular Catalysis(China)

收录：CSTPCD;;Scopus;北大核心:【北大核心2020】；CSCD:【CSCD_E2021_2022】；

基金：国家自然科学基金(21304033)。

语种：中文

中文关键词：DFT;乙炔环三聚;反应机理;TOF

外文关键词：DFT;acetylene cyclotrimerization;reaction mechanism;TOF

摘要：应用密度泛函理论(DFT)研究了Cr、Fe和Ni3种金属原子催化乙炔环三聚生成苯的反应机理.结果表明,Cr、Fe和Ni催化体系均表现出自旋翻转现象, Cr原子催化乙炔环三聚过程在自旋七重态和五重态势能面上进行,速率控制步骤为形成铬金属七元环;Fe和Ni催化体系的速率控制步骤为两分子乙炔耦合过程. Cr催化体系表现出远高于Fe和Ni催化体系的活性,是乙炔环三聚的优选催化体系.
Density functional theory(DFT) is applied to investigate the reaction mechanism of acetylene cyclotrimerization to benzene catalyzed by Cr, Fe, and Ni. Spin-crossing was calculated to be the common phenomena for both Cr, Fe and Ni catalytic systems along the reaction pathway of acetylene cyclotrimerization. The results show that acetylene cyclotrimerization catalyzed by Cr catalytic system occurs on the septet-/quintet spin surfaces. The rate-determining step is the formation of the 7-membered metallacycle. The rate-control step of Fe and Ni catalytic systems is the formation of the 5-membered metallacycle. The results show that Cr catalytic system exhibits much higher activity than that of the Fe and Ni catalytic systems. Therefore, Cr is a good candidate for developing a novel catalytic system for acetylene cyclotrimerization to benzene.