Abstract

AbstractDesigning hydrogen evolution reaction (HER) electrocatalysts for facilitating its sluggish adsorption kinetics is crucial in generating green hydrogen via sustainable water electrolysis. Herein, a high‐performance ultra‐low Ruthenium (Ru) catalyst is developed consisting of atomically‐layered Ru nanoclusters with adjacent single Ru sites, which executs a bridging‐Ru‐H activation strategy to kinetically accelerate the HER elementary steps. Owing to its optimal electronic structure and unique adsorption configuration, the hybrid Ru catalyst simultaneously displayed a drastically reduced overpotential of 16 mV at 10 mA cm−2 as well as a low Tafel slope of 35.2 mV dec−1 in alkaline electrolyte. When further coupled with a commercial IrO2 anode catalyst, the ensembled anion‐exchange membrane water electrolyzer achievs a current density of 1.0 A cm−2 at a voltage of only 1.70 Vcell. In situ spectroscopic analysis verified that Ru single atom and atomically‐layered Ru nanoclusters in the hybrid materials play a critical role in facilitating water dissociation and weakening *H adsorption, respectively. Theoretical calculations further elucidate the underlaying mechanism, suggesting that the dissociated proton at the single atom Ru site orients itself adjacently with Ru nanoclusters in a bridged structure through targeted charge transfer, thus promoting Volmer‐Heyrovsky dynamics and boosting the HER activity.

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