Electrochemical oxygen reduction to hydrogen peroxide at practical rates in strong acidic media.

Zhang, Xiao; Zhao, Xunhua; Zhu, Peng; Adler, Zachary; Wu, Zhen-Yu; Liu, Yuanyue; Wang, Haotian · Nat Commun · 2022

basic_science · Level V

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Abstract

Electrochemical oxygen reduction to hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) in acidic media, especially in proton exchange membrane (PEM) electrode assembly reactors, suffers from low selectivity and the lack of low-cost catalysts. Here we present a cation-regulated interfacial engineering approach to promote the H<sub>2</sub>O<sub>2</sub> selectivity (over 80%) under industrial-relevant generation rates (over 400 mA cm<sup>-2</sup>) in strong acidic media using just carbon black catalyst and a small number of alkali metal cations, representing a 25-fold improvement compared to that without cation additives. Our density functional theory simulation suggests a "shielding effect" of alkali metal cations which squeeze away the catalyst/electrolyte interfacial protons and thus prevent further reduction of generated H<sub>2</sub>O<sub>2</sub> to water. A double-PEM solid electrolyte reactor was further developed to realize a continuous, selective (∼90%) and stable (over 500 hours) generation of H<sub>2</sub>O<sub>2</sub> via implementing this cation effect for practical applications.