文献类型：期刊文献

英文题名：Mechanistic Insights into Surfactant-Modulated Electrode-Electrolyte Interface for Steering H2O2 Electrosynthesis

作者：Fan, Yu[1,2];Chen, Yuxin[3];Ge, Wangxin[2];Dong, Lei[1,2];Qi, Yanbin[2];Lian, Cheng[3];Zhou, Xiaodong[1];Liu, Honglai[3];Liu, Zhen[1];Jiang, Hongliang[1,4];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]East China Univ Sci & Technol, Shanghai Engn Res Ctr Hierarch Nanomat, Sch Chem Engn, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[4]Shanghai Jiao Tong Univ, Sch Chem & Chem Engn, Dept Chem Engn, Shanghai 200240, Peoples R China

年份：2024

卷号：146

期号：11

起止页码：7575

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20241115746634);WOS:【SCI-EXPANDED(收录号:WOS:001184294600001)】；

基金：This work was supported by the National Natural Science Foundation of China (22222804 and U22B20143), 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：Additives - Dyes - Electrocatalysis - Electrodes - Electrolytes - Electrolytic reduction - Hydrogen bonds - Molecular dynamics - Proton transfer - Reaction kinetics

摘要：Electrocatalytic reactions taking place at the electrified electrode-electrolyte interface involve processes of proton-coupled electron transfer. Interfacial protons are delivered to the electrode surface via a H2O-dominated hydrogen-bond network. Less efforts are made to regulate the interfacial proton transfer from the perspective of interfacial hydrogen-bond network. Here, we present quaternary ammonium salt cationic surfactants as electrolyte additives for enhancing the H2O2 selectivity of the oxygen reduction reaction (ORR). Through in situ vibrational spectroscopy and molecular dynamics calculation, it is revealed that the surfactants are irreversibly adsorbed on the electrode surface in response to a given bias potential range, leading to the weakening of the interfacial hydrogen-bond network. This decreases interfacial proton transfer kinetics, particularly at high bias potentials, thus suppressing the 4-electron ORR pathway and achieving a highly selective 2-electron pathway toward H2O2. These results highlight the opportunity for steering H2O-involved electrochemical reactions via modulating the interfacial hydrogen-bond network.