▎ 摘　　要

The Ni-based catalysts are considered to be the most promising non-noble metal catalysts for the hydrogen oxidation reaction (HOR) in alkaline fuel cells (AFCs). However, their further optimization is restricted by the unclear HOR mechanism. In this work, the density functional theory calculations were carried out to study the alkaline HOR on pure Ni-13 and Ni(13 )supported on graphene (Ni-13/G) and B- and N-doped graphene (Ni-13/BG and Ni-13/NG). The calculations indicate that the HOR proceeds preferentially through the Tafel-Volmer mechanism, in which the adsorption of H* plays a dominant role in the HOR activity. The graphene support and B/N dopants can apparently lower the d-band center of Ni-13, thereby weakening the adsorption of H*, which leads to the HOR activity sequence of Ni-13 < Ni-13/G < Ni-13/BG < Ni-13/NG. Furthermore, compared to pure Ni-13, the oxidation resistance of Ni-13/G, Ni-13/BG and Ni-13/NG is also improved via elevating onset potential of the OH* phase and reducing energy barriers of the OH* reduction with H* and H-2* . An efficient way to improve the HOR performance is tuning the adsorption of H* to accelerate the HOR rate and regulating the adsorption of OH* to enhance the antioxidant capacity.