Density functional theory studies on the mechanism of activation of methane by homonuclear bimetallic Ni-Ni

作者：Yang Jing^*; Miao Jiankui; Li Xuejiao; Xu Wenguo

来源：Computational and Theoretical Chemistry, 2012, 996: 117-124.

DOI：10.1016/j.comptc.2012.07.026

• Reaction mechanism
• Methane activation
• Homonuclear bimetallic Ni-Ni
• Isomerization reaction
• H-2 elimination reaction

The reaction mechanisms of methane catalyzed by homonuclear bimetallic Ni-Ni have been investigated theoretically in this paper. Activation of methane by homonuclear bimetallic Ni-Ni is proposed to proceed in two effective catalytic reaction routes, Route I and Route II. The homonuclear bimetallic Ni-Ni inserts in the C-H bond to form the ring-hydride and chain-hydride in Route I and Route II, respectively. In this study, we examine the isomerization reaction pathway for ring-hydride (Route I). Undergoing the isomerization reaction, the chain-product CH3Ni-Ni-H is formed. From the chain-hydride CH3Ni2-H, two kinds of distinguishable reaction paths have been considered including isomerization reaction and H-2 elimination reactions in Route II. The H-2 elimination reactions are proposed to proceed along three parallel reaction pathways with the activation of the second C-H bond on the potential energy surfaces (PESs). The pathway of rearranging to isomer in Route II is preferred to the others. In comparison with heteronuclear bimetallic NiM+ (M = Cu, Ag) and homonuclear bimetallic Pt-2(+), the dehydrogenation of methane induced by homonuclear bimetallic Ni-Ni should be more favored thermodynamically and should give more branching.

• 出版日期2012-9-15
• 单位北京理工大学; 唐山师范学院