Citation: ZHAO Jun-Feng, SUN Xiao-Li, LI Ji-Lai, HUANG Xu-Ri. Theoretical Study of Methanol C―H and O―H Bond Activation by PtRu Clusters[J]. Acta Physico-Chimica Sinica, ;2015, 31(6): 1077-1085. doi: 10.3866/PKU.WHXB201504014 shu

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

1.
Institute of Theoretical Chemistry, Jilin University, Changchun 130023, P. R. China

Received Date: 6 February 2015
Available Online: 1 April 2015
Fund Project: 国家重点基础研究发展规划项目(973) (2012CB932800) (973) (2012CB932800)国家自然科学基金(21103064, 21473070)资助 (21103064, 21473070)

Density functional theory calculations were performed to study the mechanism and reactivity of methanol oxidation mediated by Pt_nRu_m (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.
- Density functional theory,
- Cluster,
- Methanol,
- Reactivity,
- Proton transfer
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