Selective Adsorption Behavior Modulation on Nickel Selenide by Heteroatom Implantation and Heterointerface Construction Achieves Efficient Co‐production of H2 and Formate

Abstract Glycerol‐assisted hybrid water electrolysis is a potential strategy to achieve energy‐efficient hydrogen production. However, the design of an efficient catalyst for the specific reaction is still a key challenge, which suffers from the barrier of regulating the adsorption characteristics of distinctive intermediates in different reactions. Herein, a novel rationale that achieves selective adsorption behavior modulation for self‐supported nickel selenide electrode by heteroatom implantation and heterointerface construction through electrodeposition is developed, which can realize nichetargeting optimization on hydrogen evolution reaction (HER) and glycerol oxidation reaction (GOR), respectively. Specifically, the prepared Mo‐doped Ni 3 Se 2 electrode exhibits superior catalytic activity for HER, while the NiSe‐Ni 3 Se 2 electrode exhibits high Faradaic efficiency (FE) towards formate production for GOR. A two‐electrode electrolyzer exhibits superb activity that only needs an ultralow cell voltage of 1.40 V to achieve 40 mA cm −2 with a high FE (97%) for formate production. Theoretical calculation unravels that the introduction of molybdenum contributes to the deviation of the d‐band center of Ni 3 Se 2 from the Fermi level, which is conducive to hydrogen desorption. Meanwhile, the construction of the heterojunction induces the distortion of the surface structure of nickel selenide, which exposes highly active nickel sites for glycerol adsorption, thus contributing to the excellent electrocatalytic performance.