物理化学学报 >> 2015, Vol. 31 >> Issue (6): 1077-1085.doi: 10.3866/PKU.WHXB201504014

理论与计算化学 上一篇    下一篇

铂钌团簇活化甲醇C―H和O―H键的理论研究

赵俊凤, 孙小丽, 李吉来, 黄旭日   

  1. 吉林大学理论化学研究所, 长春130023
  • 收稿日期:2015-02-06 修回日期:2015-03-30 发布日期:2015-06-05
  • 通讯作者: 李吉来, 黄旭日 E-mail:jilai@jlu.edu.cn
  • 基金资助:

    国家重点基础研究发展规划项目(973) (2012CB932800)和国家自然科学基金(21103064, 21473070)资助

Theoretical Study of Methanol C―H and O―H Bond Activation by PtRu Clusters

ZHAO Jun-Feng, SUN Xiao-Li,LI Ji-Lai, HUANG Xu-Ri   

  1. Institute of Theoretical Chemistry, Jilin University, Changchun 130023, P. R. China
  • Received:2015-02-06 Revised:2015-03-30 Published:2015-06-05
  • Contact: LI Ji-Lai, HUANG Xu-Ri E-mail:jilai@jlu.edu.cn
  • Supported by:

    The project was supported by the National Key Basic Research Program of China (973) (2012CB932800) and National Natural Science Foundation of China (21103064, 21473070).

摘要:

采用密度泛函理论研究了PtnRum (n+m=3, n≠0)团簇活化甲醇C―H和O―H键的反应活性和机理. 分别给出以O―H和C―H键活化为初始步骤的势能曲线. 计算结果表明反应是以C―H键的活化为初始步骤; 三种团簇与甲醇反应的活性顺序为Pt2Ru>Pt3>PtRu2. 前线轨道分析表明PtnRum团簇活化初始的C―H和O―H键的活化过程是质子转移(PT). 此外还讨论了溶剂化对反应的影响. 本研究可为C―H键和O―H键的活化提供更深入的理解, 为甲醇活化反应催化剂选择以及其使用条件的优化提供新思路.

关键词: 密度泛函理论, 团簇, 甲醇, 活性, 质子转移

Abstract:

Density functional theory calculations were performed to study the mechanism and reactivity of methanol oxidation mediated by PtnRum (n+m=3, n≠0) clusters. The potential energy surfaces and pathways of the initial O―H and C―H bond activations were predicted. The results show that the activation of methanol proceeds preferentially along the C―H bond activation pathway. The calculated reactivity order was Pt2Ru>Pt3> PtRu2. Frontier molecular orbital analysis showed that the initial C/O―H bond activation is a proton transfer process. The solvent effect was also investigated. This study will enable a deeper understanding of C/O―H bond activation and provide new ideas for catalyst selection and optimizing conditions for methanol activation.

Key words: Density functional theory, Cluster, Methanol, Reactivity, Proton transfer

MSC2000: 

  • O641