Cu_2^-催化CO氧化反应机理的理论研究  

Theoretical Study on Mechanism of Cu_2^--Catalyzed CO Oxidation

作　　者：唐典勇[1] 胡建平[1] 张元勤[1] 胡常伟[2] 

机构地区：[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

出　　处：《化学学报》2010年第14期1379-1384,共6页Acta Chimica Sinica

基　　金：四川省自然科学基金(No2008JY0119);四川教育厅(No07ZA158)资助项目

摘　　要：用量子化学密度泛函方法详细研究了双原子铜阴离子Cu-2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Cu-2,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0.02eV.最难进行的反应通道为CO从Cu2O-2摘取氧原子形成CO2.Cu-2催化CO氧化反应活性比Au-2好.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 species（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 feasible pathway is initiated from the co-absorption of CO and O2 on Cu2^-,followed by the formation of four-membered ring intermediate to produce the corresponding products.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^-.

关 键 词：铜团簇阴离子 CO氧化反应 反应机理 密度泛函理论 

分 类 号：O643.12[理学—物理化学]