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

Wen, Yunzhou; Liu, Cheng; Huang, Rui; Zhang, Hui; Li, Xiaobao; García de Arquer, F Pelayo; Liu, Zhi; Li, Youyong et al. · Nat Commun · 2022

basic_science · Level V

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Abstract

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 (RuO<sub>2</sub>) 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<sub>x</sub>) into the RuO<sub>2</sub>. 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<sup>-2</sup>) and low degradation rate (0.014 mV h<sup>-1</sup>) 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).