Abstract

Abstract Although electrocatalysts based on transition metal phosphides (TMPs) with cationic/anionic doping have been widely studied for hydrogen evolution reaction (HER), the origin of performance enhancement still remains elusive mainly due to the random dispersion of dopants. Herein, we report a controllable partial phosphorization strategy to generate CoP species within the Co‐based metal‐organic framework (Co‐MOF). Density functional theory calculations and experimental results reveal that the electron transfer from CoP to Co‐MOF through N‐P/N‐Co bonds could lead to the optimized adsorption energy of H 2 O (Δ G ) and hydrogen (Δ G H* ), which, together with the unique porous structure of Co‐MOF, contributes to the remarkable HER performance with an overpotential of 49 mV at a current density of 10 mA cm −2 in 1 m phosphate buffer solution (PBS, pH 7.0). The excellent catalytic performance exceeds almost all the documented TMP‐based and non‐noble‐metal‐based electrocatalysts. In addition, the CoP/Co‐MOF hybrid also displays Pt‐like performance in 0.5 m H 2 SO 4 and 1 m KOH, with the overpotentials of 27 and 34 mV, respectively, at a current density of 10 mA cm −2 .