文献类型：期刊文献

英文题名：Polyelectrolyte Additive-Modulated Interfacial Microenvironment Boosting CO2 Electrolysis in Acid

作者：Wang, Anqi[1];Ge, Wangxin[1,2];Sun, Wen[1];Sheng, Xuedi[1];Dong, Lei[1];Zhang, Wenfei[1];Jiang, Hongliang[1];Li, Chunzhong[1,2,3]

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]Shanghai Jiao Tong Univ, Sch Chem & Chem Engn, Dept Chem Engn, Shanghai 200240, Peoples R China

年份：2025

卷号：64

期号：1

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20244417272298);WOS:【SCI-EXPANDED(收录号:WOS:001341402600001)】；

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：acidic CO2 electroreduction; electrode-electrolyte interface; hydrogen-bond; polyelectrolyte; in situ spectroscopy

摘要：Acidic CO2 electrolysis offers a promising strategy to achieve high carbon utilization and high energy efficiency. However, challenges still remain in suppressing the competitive hydrogen evolution reaction (HER) and improving product selectivity. Although high concentrations of potassium ions (K+) can suppress HER and accelerate CO2 reduction, they still inevitably suffer from salt precipitation problems. In this study, we demonstrate that the sulfonate-based polyelectrolyte, polystyrene sulfonate (PSS), enables to reconstruct the electrode-electrolyte interface to significantly enhance the acidic CO2 electrolysis. Mechanistic studies reveal that PSS induces high local K+ concentrations through the electrostatic interaction between PSS anions and K+. In situ spectroscopy reveals that PSS reshapes the interfacial hydrogen-bond (H-bond) network, which is attributed to the H-bonds between PSS anions and hydrated proton, as well as the steric hindrance of the additive molecules. This greatly weakens proton transfer kinetics and leads to the suppression of undesirable HER. As a result, a Faradaic efficiency of 93.9 % for CO can be achieved at 250 mA cm(-2), simultaneous with a high single-pass carbon efficiency of 72.2 % on commercial Ag catalysts in acid. This study highlights the important role of the electrode-electrolyte interface induced by polyelectrolyte additives in promoting electrocatalytic reactions.