气相中Co+催化N2O与C2H6循环反应催化剂活性的理论研究

doi:10.1016/S1872-2067(14)60037-1

催化学报 ›› 2014, Vol. 35 ›› Issue (4): 579-589.DOI: 10.1016/S1872-2067(14)60037-1

气相中Co⁺催化N₂O与C₂H₆循环反应催化剂活性的理论研究

吴晶晶, 王永成, 蔡君, 金燕子, 王环江, 甘延珍

西北师范大学化学化工学院, 甘肃兰州730070

收稿日期:2013-11-18 修回日期:2014-01-15 出版日期:2014-03-20 发布日期:2014-03-21
通讯作者: 王永成
基金资助:
国家自然科学基金（21263023）.

Theoretical investigation into the Co⁺ catalytic activity in the cycle reaction of N₂O with C₂H₆ in the gas phase

Jingjing Wu, Yongcheng Wang, Jun Cai, Yanzi Jin, Huanjiang Wang, Yanzhen Gan

Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, Gansu, China

Received:2013-11-18 Revised:2014-01-15 Online:2014-03-20 Published:2014-03-21
Supported by:
This work was supported by the National Natural Foundation of China (21263023).

摘要/Abstract

摘要：

采用密度泛函理论UB3LYP方法对Co⁺在三重态及五重态势能面上催化N₂O与C₂H₆进行循环反应的两态反应机理进行了研究. 运用Harvery方法优化了两自旋态势能面5个最低能量交叉点（MECP），计算了MECP处自旋-轨道耦合作用. 采用Landau-Zener公式计算了自旋翻转处的系间窜越几率，各MECP处均可发生有效系间窜越. 通过应用Kozuch提出的能量跨度模型，Co⁺催化N₂O与C₂H₆在298K下反应生成CH₃CHO时有最大的TOF值3.35×10^-21s^-1.

关键词: 一氧化二氮, 乙烷, 循环反应, 密度泛函, 两态反应, 系间窜越, 能量跨度, 转化频率

Abstract:

The spin-forbidden mechanism of the reaction between N₂O and C₂H₆ catalyzed by Co⁺ has been investigated using UB3LYP density functional theory. The Harvey method has been applied to optimize five minimum energy crossing points (MECP) on both triplet and quintet potential energy surfaces. Possible spin inversion processes are discussed by means of spin-orbit coupling calculations. According to the calculation of probability of electron hopping using the Landau-Zener formula, effective intersystem crossing may occur at each MECP. The energetic span model proposed by Kozuch has been applied to the catalytic cycles, and shows the turnover frequency reaches 3.35×10^-21 s^-1 when Co⁺ catalyzes the reaction to produce CH₃CHO at 298K.

Key words: Nitrogen monoxide, Ethane, Cycle reaction, Density functional theory, Two-state reaction, Intersystem cross, Energetic span, Turnover frequency

吴晶晶, 王永成, 蔡君, 金燕子, 王环江, 甘延珍. 气相中Co⁺催化N₂O与C₂H₆循环反应催化剂活性的理论研究[J]. 催化学报, 2014, 35(4): 579-589.

Jingjing Wu, Yongcheng Wang, Jun Cai, Yanzi Jin, Huanjiang Wang, Yanzhen Gan. Theoretical investigation into the Co⁺ catalytic activity in the cycle reaction of N₂O with C₂H₆ in the gas phase[J]. Chinese Journal of Catalysis, 2014, 35(4): 579-589.

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气相中Co⁺催化N₂O与C₂H₆循环反应催化剂活性的理论研究

Theoretical investigation into the Co⁺ catalytic activity in the cycle reaction of N₂O with C₂H₆ in the gas phase

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