Alleviating OH Blockage on the Catalyst Surface by the Puncture Effect of Single-Atom Sites to Boost Alkaline Water Electrolysis.

Nonprecious transition metal catalysts have emerged as the preferred choice for industrial alkaline water electrolysis due to their cost-effectiveness. However, their overstrong binding energy to adsorbed OH often results in the blockage of active sites, particularly in the cathodic hydrogen evolution reaction. Herein, we found that single-atom sites exhibit a puncture effect to effectively alleviate OH blockades, thereby significantly enhancing the alkaline hydrogen evolution reaction (HER) performance. Typically, after anchoring single Ru atoms onto tungsten carbides, the overpotential at 10 mA·cm is reduced by more than 130 mV (159 vs 21 mV). Also, the mass activity is increased 16-fold over commercial Pt/C (MA = 17.3 A·mg vs 1.1 A·mg, Pt/C). More importantly, such electrocatalyst-based alkaline anion-exchange membrane water electrolyzers can exhibit an ultralow potential (1.79 V) and high stability at an industrial current density of 1.0 A·cm. Density functional theory (DFT) calculations reveal that the isolated Ru sites could weaken the surrounding local OH binding energy, thus puncturing OH blockage and constructing bifunctional interfaces between Ru atoms and the support to accelerate water dissociation. Our findings exhibit generality to other transition metal catalysts (such as Mo) and contribute to the advancement of industrial-scale alkaline water electrolysis.