Acta Phys. -Chim. Sin. ›› 2015, Vol. 31 ›› Issue (6): 1077-1085.doi: 10.3866/PKU.WHXB201504014


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
  • 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).


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