Asymmetrically coordinated nickel‐based catalysts for enhanced hydrogen evolution reaction

Abstract

Developing non‐noble metal hydrogen evolution reaction (HER) catalysts with high efficiency for water dissociation in alkaline environments is crucial for achieving cost‐effective alkaline water electrolyzer. Surface engineering offers immense potential to design promising HER catalysts with enhanced performance, but it faces multiple challenges such as optimizing hydrogen adsorption energy. Herein, Ni‐based hydroxide catalysts doped with heteroatoms are synthesized via electrodeposition, forming a Co‐doped asymmetric S–Ni–F coordination structure, which requires the overpotential of only 20 mV to reach a current density of −10 mA cm⁻², and remains stable for over 100 h at −0.5 A cm⁻². DFT calculations reveal that sulfur and fluorine doping could effectively mitigate the energy associated with active hydrogen adsorption and facilitate water molecule dissociation. Furthermore, the electron coupling within the d‐orbital of the Ni–O–Co structure further amplifies the catalytic efficacy. This asymmetric structure offering a pathway for designing high‐efficiency and non‐noble metal alkaline HER catalysts.