Local Charge Transfer Unveils Antideactivation of Ru at High Potentials for the Alkaline Hydrogen Oxidation Reaction.

The activity of Ru-based alkaline hydrogen oxidation reaction (HOR) electrocatalysts usually decreases rapidly at potentials higher than 0.1 V ( vs a reversible hydrogen electrode (RHE)), which significantly limits the lifetime of fuel cells. It is found that this phenomenon is caused by the overadsorption of the O species due to the overcharging of Ru nanoparticles at high potentials. Here, Mn 1 O x (OH) y clusters-modified Ru nanoparticles (Mn 1 O x (OH) y @Ru/C) were prepared to promote charge transfer from overcharged Ru nanoparticles to Mn 1 O x (OH) y clusters. Mn 1 O x (OH) y @Ru/C exhibits high HOR activity and stability over a wide potential range of 0-1.0 V. Moreover, a hydroxide exchange membrane fuel cell with a Mn 1 O x (OH) y @Ru/C anode delivers a high peak power density of 1.731 W cm -2 , much superior to that of a Pt/C anode. In situ X-ray absorption fine structure (XAFS) analysis and density functional theory (DFT) calculations reveal that Mn in Mn 1 O x (OH) y clusters could receive more electrons from overcharged Ru at higher potentials and significantly decrease the overadsorption of the O species on Ru, thus permitting the HOR on Ru to proceed at high potentials. This study provides guidance for the design of alkaline HOR catalysts without activity decay at high potentials.