Cation‐Vacancy‐Enriched Nickel Phosphide for Efficient Electrosynthesis of Hydrogen Peroxides

Electrocatalytic hydrogen peroxide (H₂ O₂ ) synthesis via the two-electron oxygen reduction reaction (2e ORR) pathway is becoming increasingly important due to the green production process. Here, cationic vacancies on nickel phosphide, as a proof-of-concept to regulate the catalyst's physicochemical properties, are introduced for efficient H₂ O₂ electrosynthesis. The as-fabricated Ni cationic vacancies (V_Ni )-enriched Ni_{2- x} P-V_Ni electrocatalyst exhibits remarkable 2e ORR performance with H₂ O₂ molar fraction of >95% and Faradaic efficiencies of >90% in all pH conditions under a wide range of applied potentials. Impressively, the as-created V_Ni possesses superb long-term durability for over 50 h, suppassing all the recently reported catalysts for H₂ O₂ electrosynthesis. Operando X-ray absorption near-edge spectroscopy (XANES) and synchrotron Fourier transform infrared (SR-FTIR) combining theoretical calculations reveal that the excellent catalytic performance originates from the V_Ni -induced geometric and electronic structural optimization, thus promoting oxygen adsorption to the 2e ORR favored "end-on" configuration. It is believed that the demonstrated cation vacancy engineering is an effective strategy toward creating active heterogeneous catalysts with atomic precision.