Controllable Detachment of Organic Ligands on Ultrathin Amorphous Nanosheets Tailors the Electron‐Aggregation for Accelerated pH‐Universal Hydrogen Reaction

Abstract Tailoring the local environment of catalyst surface has emerged as an effective strategy to enhance the reaction kinetics involving multiple intermediates. For hydrogen evolution reactions (HER), the driving factors for hydrogen aggregation and migration which are poorly understood in depth affects the reaction kinetics especially over a wide pH range. Inspired by the selectivity of the catalyst surface microenvironment for intermediates, an interfacial electrocatalyst composed of Ru ultrafine nanocatalysts anchored onto monolayer amorphous (a‐WCoNiO) nanosheets with electron‐rich microenvironment induced by an organic oleylamine ligand is designed to realize high‐performance pH‐universal HER. This Ru/a‐WCoNiO possesses impressively low overpotentials of ‐13, ‐14, and ‐14 mV at 10 mA cm ⁻² in 0.5 m H ₂ SO ₄ , 1 m KOH and 1 m PBS, respectively, ranking among the best HER catalysts reported to date. Benefiting from the electron‐rich microenvironment, the Ru/a‐WCoNiO exhibits record‐high turnover frequency (TOF) and mass activity (MA), which is more than 47.9 times higher than that of commercial 20% Pt/C. Importantly, other precious metals are loaded on a‐WCoNiO and enhancing their mass current density for pH‐universal HER. It is believed that this developed approach of organic modifiers tailored local microenvironment has practical significance and advantages for designing other high‐performance catalysts.