文献类型：期刊文献

英文题名：Mercaptoimidazole-Engineered Microenvironment Enables Durable CO2 Electroreduction in a Zero-Gap PEM Electrolyzer

作者：Wu, Jia Chen[1];Yu, Tingting[2,3];Gu, Jianming[1];Fu, Huai Qin[4];Ye, Ziwei[5];Yuan, Hai Yang[1];Lian, Cheng[2,3];Cao, Huiliang[1];Yang, Hua Gui[1];Liu, Peng Fei[1]

机构：[1]East China Univ Sci & Technol, Sch Mat Sci & Engn, Key Lab Ultrafine Mat, Minist Educ, Shanghai, Peoples R China;[2]East China Univ Sci & Technol, Shanghai Engn Res Ctr Hierarch Nanomat, Sch Chem Engn, State Key Lab Chem Engn, Shanghai, Peoples R China;[3]East China Univ Sci & Technol, Sch Chem & Mol Engn, Shanghai, Peoples R China;[4]Griffith Univ, Sch Environm & Sci, Gold Coast Campus, Gold Coast, Qld, Australia;[5]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Sch Chem & Mol Engn, Key Lab Adv Mat,Joint Int Res Lab Precis Chem & Mo, Shanghai, Peoples R China

年份：2026

外文期刊名：ADVANCED MATERIALS

收录：;EI(收录号：20262320865822);WOS:【SCI-EXPANDED(收录号:WOS:001784512000001)】；

基金：This work was financially supported by the National Natural Science Foundation of China (22379043 and 22239001), the Shanghai Pilot Program for Basic Research (22TQ1400100-12), the Science and Technology Commission of Shanghai Municipality (23520710700 and 25DZ3000301), and the Fundamental Research Funds for the Central Universities. The authors also thank the Frontiers Science Center for Materiobiology and Dynamic Chemistry, the crew of the BL14W1 beamline at the Shanghai Synchrotron Radiation Facility (SSRF) for their constructive assistance with the XAFS measurements and data analyses.

语种：英文

外文关键词：acid CO2 electroreduction; formate; ligand modification; local microenvironment; proton exchange membrane electrolyzer

摘要：CO2 conversion in proton exchange membrane (PEM) electrolysis systems offers a sustainable pathway for chemical production by eliminating carbonate formation; however, it faces a trade-off between suppressing the hydrogen evolution reaction and preventing salt precipitation. Here, we resolve this paradox through a molecular-level engineering strategy by anchoring a mercaptoimidazole ligand on lead-based catalyst. Operando spectroscopic analyses and theoretical studies reveal that this ligand shell creates a local alkaline microenvironment and establishes a proton-shielding effect at the catalyst surface. When integrated into a zero-gap PEM electrolyzer, the catalyst achieves a peak formate Faradaic efficiency of 95.8% and sustains over 90% selectivity at a current density of 600 mA cm-2. This performance persists under strongly acidic (pH 1.0) and cation-starved (0.001 M) conditions. The PEM system delivers extended stability, with over 300 h of continuous operation at industrially relevant current densities. Our work establishes a design strategy that decouples the catalytic microenvironment from the bulk electrolyte and provides a route for durable and selective acidic CO2 electrolyzers.