Highly durable Volmer-Heyrovsky hydrogen evolution reaction in alkaline media

Reducing high overpotentials in the alkaline water reduction reaction is critical for renewable hydrogen storage. Here, we report a dual-site catalytic center comprising oxygen-bridging Fe–OH and Ni–O (FeOH–O–NiO) with Pt-like activity, where frustrated Fe–OH Lewis acid and Ni–O Lewis base generate a strong electrostatic field to promote water dissociation (Volmer step: H2O + e− → Had* + OH−). The resulting Had* adsorbs on Ni–O, forming Ni–OHad, while Fe–OH and Ni–OHad synergistically drive the Heyrovsky step (Had* + H2O + e− → H2 + OH−) to produce H2. This process achieves ultralow overpotential (52 mV @ 10 mA cm−2) and exceptional stability (>1000 h@300 mA cm−2), offering a design strategy for low-cost and high-performance hydrogen evolution reaction catalysts.