Oriented Functional Division of Asymmetric W–V Dual Sites in NiFe LDH Enables Oxygen Evolution at Industrial-Grade Current Densities

Abstract Oxygen evolution reaction (OER) remains the dominant energy-loss step in industrial water electrolysis for hydrogen production. NiFe-layered double hydroxides (NiFe LDH) are widely used as non-noble OER catalysts, but their performance is fundamentally limited by the slow initial *OH deprotonation and unfavorable *OOH intermediate adsorption. Herein, we propose a functionally asymmetric dual-site strategy with oriented functional division to overcome this limitation, in which two distinct dopant sites are assigned different functions to independently optimize contradictory elementary steps. Vanadium (V) dopants generate abundant oxygen vacancies as dedicated proton acceptors, reducing the energy barrier for *OH deprotonation and shifting the rate-determining step (RDS) from *OH→*O to *OOH→O2. Tungsten (W) dopants act as electronic modulators to regulate the d-band center of Ni active sites, optimizing *OOH adsorption without compromising the acceleration effect of V sites. This decoupled optimization results in a low Tafel slope of 45.07 mV dec–1, a low overpotential of 244 mV at 50 mA cm–2, and under industrial-grade conditions of 1 A cm–2, the catalyst maintains stability for 200 h. This work presents a site-selective functional division paradigm that decouples contradictory elementary steps, offering a route to designing multi-component electrocatalysts.