Introducing Brønsted acid sites to accelerate the bridging-oxygen-assisted deprotonation in acidic water oxidation

Oxygen evolution reaction (OER) consists of four sequential proton-coupled electron transfer steps, which suffer from sluggish kinetics even on state-of-the-art ruthenium dioxide (RuO₂) catalysts. Understanding and controlling the proton transfer process could be an effective strategy to improve OER performances. Herein, we present a strategy to accelerate the deprotonation of OER intermediates by introducing strong Brønsted acid sites (e.g. tungsten oxides, WO_x) into the RuO₂. The Ru-W binary oxide is reported as a stable and active iridium-free acidic OER catalyst that exhibits a low overpotential (235 mV at 10 mA cm^-2) and low degradation rate (0.014 mV h^-1) over a 550-hour stability test. Electrochemical studies, in-situ near-ambient pressure X-ray photoelectron spectroscopy and density functional theory show that the W-O-Ru Brønsted acid sites are instrumental to facilitate proton transfer from the oxo-intermediate to the neighboring bridging oxygen sites, thus accelerating bridging-oxygen-assisted deprotonation OER steps in acidic electrolytes. The universality of the strategy is demonstrated for other Ru-M binary metal oxides (M = Cr, Mo, Nb, Ta, and Ti).