Fan, LeiBai, XiaowanXia, ChuanZhang, XiaoZhao, XunhuaXia, YangWu, Zhen-YuLu, YingyingLiu, YuanyueWang, Haotian2022-08-042022-08-042022Fan, Lei, Bai, Xiaowan, Xia, Chuan, et al.. "CO2/carbonate-mediated electrochemical water oxidation to hydrogen peroxide." <i>Nature Communications,</i> 13, (2022) Springer Nature: https://doi.org/10.1038/s41467-022-30251-5.https://hdl.handle.net/1911/112982Electrochemical water oxidation reaction (WOR) to hydrogen peroxide (H2O2) via a 2e− pathway provides a sustainable H2O2 synthetic route, but is challenged by the traditional 4e− counterpart of oxygen evolution. Here we report a CO2/carbonate mediation approach to steering the WOR pathway from 4e− to 2e−. Using fluorine-doped tin oxide electrode in carbonate solutions, we achieved high H2O2 selectivity of up to 87%, and delivered unprecedented H2O2 partial currents of up to 1.3 A cm−2, 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 H2O2 through the formation of carbonate radical and percarbonate intermediates. The high selectivity, industrial-relevant activity, and good durability open up practical opportunities for delocalized H2O2 production.engThis article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder.Journal articles41467-022-30251-5https://doi.org/10.1038/s41467-022-30251-5