Understanding the reactivity of the tetrahedrally coordinated high-valence d(0) transition metal oxides toward the C-H bond activation of alkanes: A cluster model study

作者：Fu, Gang; Chen, Zhe-Ning; Xu, Xin^*; Wan, Hui-Lin

来源：Journal of Physical Chemistry A, 2008, 112(4): 717-721.

DOI：10.1021/jp709651n

• COUPLED ELECTRON-TRANSFER
• DENSITY-FUNCTIONAL THEORY
• HYDROGEN-ATOM ABSTRACTION
• SELECTIVE OXIDATION
• CATALYTIC PROPERTIES
• BISMUTH MOLYBDATES
• METHANE ACTIVATION
• V2O5(010) SURFACE
• MOLYBDENUM
• ADSORPTION

We have carried out a theoretical study on the structure-function relationship for the selective oxidation of lower alkanes (C-1-C-4). The H abstraction mechanism has been examined over the model catalysts of high-valence d(0) transition metal oxides in the tetrahedral coordination. The intrinsic connections among the H abstraction barrier, the strengths of the O-H and the M-O bonds, the ability of electron transfer, as well as the energy gap of frontier orbitals of the oxides have been rationalized in terms of thermodynamics cycles and the frontier orbital analysis. In particular, we emphasize the role that the O-H bond strength plays in determining the reactivity of a metal oxide.

• 出版日期2008-1-31
• 单位厦门大学