CO<sub>2</sub>/carbonate-mediated electrochemical water oxidation to hydrogen peroxide.

Fan, Lei; Bai, Xiaowan; Xia, Chuan; Zhang, Xiao; Zhao, Xunhua; Xia, Yang; Wu, Zhen-Yu; Lu, Yingying et al. · Nat Commun · 2022

basic_science · Level V

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Abstract

Electrochemical water oxidation reaction (WOR) to hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) via a 2e<sup>-</sup> pathway provides a sustainable H<sub>2</sub>O<sub>2</sub> synthetic route, but is challenged by the traditional 4e<sup>-</sup> counterpart of oxygen evolution. Here we report a CO<sub>2</sub>/carbonate mediation approach to steering the WOR pathway from 4e<sup>-</sup> to 2e<sup>-</sup>. Using fluorine-doped tin oxide electrode in carbonate solutions, we achieved high H<sub>2</sub>O<sub>2</sub> selectivity of up to 87%, and delivered unprecedented H<sub>2</sub>O<sub>2</sub> partial currents of up to 1.3 A cm<sup>-2</sup>, which represents orders of magnitude improvement compared to literature. Molecular dynamics simulations, coupled with electron paramagnetic resonance and isotope labeling experiments, suggested that carbonate mediates the WOR pathway to H<sub>2</sub>O<sub>2</sub> through the formation of carbonate radical and percarbonate intermediates. The high selectivity, industrial-relevant activity, and good durability open up practical opportunities for delocalized H<sub>2</sub>O<sub>2</sub> production.