Boosting Efficient Alkaline Hydrogen Evolution Reaction of CoFe‐Layered Double Hydroxides Nanosheets via Co‐Coordination Mechanism of W‐Doping and Oxygen Defect Engineering

Abstract While surface defects and heteroatom doping exhibit promising potential in augmenting the electrocatalytic hydrogen evolution reaction (HER), their performance remains unable to rival that of the costly Pt‐based catalysts. Yet, the concurrent modification of catalysts by integrating both approaches stands as a promising strategy to effectively address the aforementioned limitation. In this work, tungsten dopants are introduced into self‐supported CoFe‐layered double hydroxides (LDH) on nickel foam using a hydrothermal method, and oxygen vacancies (Ov) are further introduced through calcination. The analysis results demonstrated that tungsten doping reduces the Ov formation energy of CoFeW‐LDH. The Ov acted as oxophilic sites, facilitating water adsorption and dissociation, and reducing the barrier for cleaving HO─H bonds from 0.64 to 0.14 eV. Additionally, Ov regulated the electronic structure of CoFeW‐LDH to endow optimized hydrogen binding ability on tungsten atoms, thereby accelerating alkaline Volmer and Heyrovsky reaction kinetics. Specifically, the abundance of Ov induced a transition of tungsten from a six‐coordinated to highly active four‐coordinated structure, which becomes the active site for HER. Consequently, an ultra‐low overpotential of 41 mV at 10 mA cm −2 , and a low Tafel slope of 35 mV dec −1 are achieved. These findings offer crucial insights for the design of efficient HER electrocatalysts.