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化学学报
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化学学报 ›› 2011, Vol. 69 ›› Issue (02): 157-162. 上一篇    下一篇

研究论文

气相中2Sr＋和2Ba＋催化N2O与CO反应的计算研究

刘凤霞*,1，张建辉2，胡敏哲2，冷艳丽3，王永成4   

  1. (1定西师范高等专科学校 生化系 定西 743000)
    (2兰州资源环境职业技术学院 基础部 兰州 730021)
    (3西北永新化工股份有限公司 技术中心 兰州 730000)
    (4西北师范大学化学化工学院 甘肃省高分子材料重点实验室 兰州 730070)5. 兰州资源环境职业技术学院 基础部 兰州730021  
  • 投稿日期:2010-02-24 修回日期:2010-07-29 发布日期:2010-09-26
  • 通讯作者: 张建辉 E-mail:gszhangjh@yahoo.cn

Theoretical Study for the Reduction of N2O with CO Catalyzed by 2Sr＋ and 2Ba＋ in the Gas

Liu Fengxia*,1 Zhang Jianhui2 Hu Minzhe2 Leng Yanli3 Wang Yongcheng4   

  1. (1 Department of Biologically Chemistry, Dingxi Teacher s College, Dingxi 743000)
    (2 Department of Foundation, Lanzhou Resources & Environment Voc-Tech College, Lanzhou 730021)
    (3 Department of Technical Center, Northwest Yongxin Group Co., Ltd, Lanzhou 730000)
    (4 Gansu Key Laboratory of Polymer Materials, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070)
  • Received:2010-02-24 Revised:2010-07-29 Published:2010-09-26
  • Contact: Zhang Jian-Hui E-mail:gszhangjh@yahoo.cn

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用密度泛函理论DFT-UB3LYP方法, 对2Sr＋, 2Ba＋采用相对论校正赝势基组SDD, 对C, N, O采用6-311＋G(2d)基组, 计算研究了气相中碱土金属离子2Sr＋, 2Ba＋催化N2O (X1∑＋)＋CO (X1∑＋) → N2 (X1∑＋g)＋CO2 (X1∑＋g)反应的微观机理. 优化了二重态势能面上各反应物、中间体和过渡态的构型特征, 并用频率分析方法和内禀反应坐标方法(IRC)对过渡态进行了验证. 2Sr＋和2Ba＋转化N2O, CO为N2, CO2的循环催化反应的计算所得结论与实验结果相同, 两者的反应路径相似, 两步进行的主反应都各包括两个反应通道. 并通过分析NBO电荷分布对各反应复合物形成时电荷的变化作了相应讨论.

关键词: 2Sr＋, 2Ba＋, N2O和CO, 反应机理, 密度泛函理论(DFT)

The reaction mechanism of the reaction N2O (1∑＋)＋CO (1∑＋) → N2 (1∑＋g)＋CO2 (1∑＋g) catalyzed by alkaline-earth metal cations 2Sr＋ and 2Ba＋ have been investigated by using the UB3LYP density functional theory (DFT, UB3LYP) with the relativistic effective core potential (RECP) of basis sets (SDD) for 2Sr＋, 2Ba＋ and the 6-311＋G(2d) basis set for C, N and O on doublet energy surfaces. The geometries for reactants, the transition states and the products are completely optimized. All the transition states are verified by the vibrational analysis and the internal reaction coordinate (IRC) calculations. The results show both main reactions process in a two-step manner to products. NBO analysis has been used to discuss the structure of reactant-complexes, our calculated results for the title reactions are in close agreement with experimental observations.

Key words: 2Sr＋, 2Ba＋, N2O＋CO, reaction mechanism, density functional theory (DFT)