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化学学报
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化学学报 ›› 2010, Vol. 68 ›› Issue (14): 1379-1384. 上一篇    下一篇

研究论文

Cu2-催化CO氧化反应机理的理论研究

唐典勇*,1，胡建平1，张元勤1，胡常伟2   

  1. (1乐山师范学院化学与生命科学学院分子设计中心 乐山 614000)
    (2四川大学化学学院 成都 610064)
  • 投稿日期:2009-06-20 修回日期:2010-03-09 发布日期:2010-03-20
  • 通讯作者: 唐典勇 E-mail:qchem@189.cn

Theoretical Study on Mechanism of Cu2ˉ-Catalyzed CO Oxidation

Tang Dianyong*,1 Hu Jianping1 Zhang Yuanqin1 Hu Changwei2   

  1. (1 Molecular Design Center, College of Chemistry and Life Science, Leshan Normal University, Leshan 614000)
    (2 College of Chemistry, Sichuan University, Chengdu 610064)
  • Received:2009-06-20 Revised:2010-03-09 Published:2010-03-20
  • Contact: TANG Dian-Yong E-mail:qchem@189.cn

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用量子化学密度泛函方法详细研究了双原子铜阴离子催化CO氧化形成CO2反应在气相中机理. 在UB3LYP结合混合基组水平上, 优化了所有反应物, 中间体, 过渡态和产物的几何构型, 并进行了振动分析和波函数稳定性测试. 计算结果表明最可能反应通道为CO和O2共吸附到, 然后形成四元环中间体, 最后四元环中间体分解形成产物或另一分子CO进攻四元环中间体从而形成产物. 第二个CO分子的协同作用比较小, 能垒仅相差0.02 eV. 最难进行的反应通道为CO从摘取氧原子形成CO2. 催化CO氧化反应活性比好.

关键词: 铜团簇阴离子, CO氧化反应, 反应机理, 密度泛函理论

The reaction mechanism of CO oxidation to produce CO2 catalyzed by Cu2- in gas phase has been studied using density functional theory. By using the UB3LYP functional with the mixed basis sets level, the geometries of all spe-cies (reactants, intermediates, transition states, and products) were optimized, and the vibration frequencies as well as tests of wavefunction stability were also performed. The computational results indicate that the di-copper carbonate intermediate pathway is the easiest to occur. The most difficult pathway is that CO abstracts an oxygen atom from Cu2O2- to form product CO2. The catalytic activity of Cu2- toward CO oxidation reaction is better than that of Au2- and Ag2- .

Key words: Cu cluster anion, CO oxidation, mechanism, density functional theory