围绕电化学催化问题，综述了密度泛函理论研究电极电势、电催化剂结构与物种的吸附脱附、电子转移以及电催化剂活性、稳定性的关系. 电极电势与金属催化剂d带中心影响着电极表面物种的形成、吸附和脱附，通过催化剂合金化或表面修饰、载体-催化剂相互作用可实现催化剂d带中心的调控，寻找最优吸附强度的催化剂，以期提高催化活性；通过电极电势与催化剂的HOMO能级的调控，实现与电子受体物质LUMO能级的匹配，达到促进或抑制催化剂与电子受体物质之间电子转移的快慢.

In this review, we focus on achievements in electro-catalysis based on the density function theory study. The relationships among the electrode potential, electronic structure of catalysts and electro-catalytic activity are summarized in three parts: the adsorption and desorption of species, electron transfer, and stability of catalysts. The electrode potential and the electronic structure (d-band center or Fermi (HOMO) energy) of catalysts significantly influence the formation, adsorption and desorption of surface species on electrode. The electro-catalytic activity can be improved by modulating the electrode potential and electronic structure of catalysts.