Dimerization assembly mechanism involving proton coupled electron transfer for hydrogen evolution from water by molybdenum-oxo catalyst

•A molybdenum-oxo (Mo-oxo) compound for hydrogen generation was studied.•Novel dimerization assembly mechanism was reported in this work.•Proton-coupled electron transfer reaction after dimerization assembly plays a significant role.

In this work, the mechanism for hydrogen generation of a recently reported Mo-oxo catalyst is investigated by theoretical method. A novel dimerization assembly mechanism has been elaborated. Structural details of the Mo-oxo complex which are essential to the catalytic activity are provided. The dimerization mechanism of hydrogen production is demonstrated to be more feasible than the monomer mechanism proposed in the previous work. Furthermore, proton-coupled electron transfer (PCET) reaction in the hydrogen bond network after dimerization assembly plays a very significant role on the hydrogen evolution from water by molybdenum-oxo catalyst. This study can be useful in understanding of many catalytic processes for hydrogen generation and designing new catalysis with high efficiency.

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