Boosting Hydrogen Evolution Reaction by Sequential Modulation of Elementary Steps on Ru–Ni–P-Coated Cu Nanowires

Understanding and controlling the elementary steps in catalytic processes during electrochemical reactions are crucial for advancing sustainable energy technologies. Herein, a promising concept of designing both elementary steps (water adsorption/dissociation and adsorbed hydrogen intermediate desorption) simultaneously is proposed for a robust hydrogen evolution reaction on Ru/Ni–P@Cu. The customized structure affords superb alkaline/neutral HER activity regarding reduced overpotential of 15/26 mV at 10 mA cm–2. Notably, the alkaline/neutral HER mass activity (0.66/0.28 A mg–1) and price activity (45.66/19.34 A dollar–1) of Ru/Ni–P@Cu are 11.8/12.2 and 25.7/26.9 times higher than those of Pt/C, respectively. Experimental results and computational analyses reveal that the accessible Ru–Ni–P moieties on the interface confers the desired electronic structure, thereby promoting first elementary reaction of H2O adsorption/dissociation, and simultaneously accelerating second elementary reaction of H* intermediate desorption via a hydrogen spillover. This work affords a transformative paradigm for elevating multistep catalytic reaction kinetics and paves the way for synergistic advancements in catalyst performance and cost-effectiveness.