文献类型：期刊文献

英文题名：Tuning interfacial proton transfer for directing oxygen reduction reaction toward hydrogen peroxide

作者：Fan, Yu[1,2];Chen, Hao[1];Ge, Wangxin[2];Zhou, Xiaodong[1];Wang, Haiyan[1,3];Jiang, Hongliang[1];Li, Chunzhong[1,2,4]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, Key Lab Ultrafine Mat, Minist Educ, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Shanghai Engn Res Ctr Hierarch Nanomat, Sch Mat Sci & Engn, Shanghai 200237, Peoples R China;[3]Henan Normal Univ, Ctr Henan Prov Green Mfg Fine Chem, Sch Chem & Chem Engn, Key Lab Green Chem Media & React,Minist Educ, Xinxiang 453007, Peoples R China;[4]Shanghai Jiao Tong Univ, Sch Chem & Chem Engn, Dept Chem Engn, Shanghai 200240, Peoples R China

年份：2025

卷号：12

期号：11

外文期刊名：NATIONAL SCIENCE REVIEW

收录：;EI(收录号：20254619511659);WOS:【SCI-EXPANDED(收录号:WOS:001613882000001)】；

基金：This work was supported by the National Natural Science Foundation of China (22222804, U24A20546, U22B20143 and 22208088), the National Key R&D program (2022YFB3808400), the Science and Technology Commission of Shanghai Municipality (22dz1205900), and the Shanghai Municipal Science and Technology Major Project.

语种：英文

外文关键词：proton transfer; H2O2 electrosynthesis; solvation structure; hydrogen-bond network; electrolyte

摘要：Proton transfer at the electrified interface plays a pivotal role in proton-coupled electron transfer (PCET) reactions. However, tuning the interfacial proton transfer through the electrolyte remains a largely unexplored yet effective approach for boosting electrochemical performance. Here, we demonstrate that the chelation strength of chelating molecules can serve as a criterion for selecting alkaline electrolyte additives to direct the oxygen reduction reaction (ORR) toward hydrogen peroxide (H2O2) electrosynthesis. We reveal that chelating molecules enter the solvation shell of cations, disrupting the long-range connectivity of hydrogen-bond networks by forming rigid near-range hydrogen bonds. The hydrogen-bond networks serve as a channel for proton transfer through hopping. These reshaped hydrogen-bond networks slow down the proton transfer process. Subsequently, ethylenediaminetetraacetic acid (EDTA), with its high chelation strength, finely regulates proton availability at the electrified interface. This modulation effectively decelerates the 4e(-)-involved PCET kinetics, steering the ORR toward the 2e(-) pathway of a lower energy barrier. As a result, EDTA-containing electrolytes achieve significantly higher H2O2 selectivity and Faradaic efficiency than other systems. This work underscores the importance of the interfacial hydrogen-bond networks in electrochemical reaction kinetics and could guide the design of electrolytes for various electrochemical reactions.