Electrocatalytic C─S Cross‐Coupling via Engineered Frustrated Lewis Acid‐Base Pairs for High‐Efficiency Methanesulfonate Synthesis

作者：Yuhang Gao, Menglong Sun, Jing Yuan, Kaiheng Zhao, Lili Chen, Yangyang Guo, Zhiqin Liang, Yijun Yang, Fangli Yuan, Tingyu Zhu, Xi Wang, Jiannian Yao · 发表于：Angewandte Chemie International Edition · 年份：2025 · DOI：10.1002/anie.202509851 · 被引用次数：11 · 研究领域：Sulfur-Based Synthesis Techniques、Chemical Synthesis and Reactions、Advanced Photocatalysis Techniques

Abstract The electrochemical synthesis of sulfonyl compounds under mild conditions remains a significant challenge due to the reliance on harsh reagents, high energy consumption, and low selectivity in conventional methods. Herein, we report a novel strategy for efficient C─S bond formation through in situ modulation of frustrated Lewis acid‐base pairs within a copper‐based metal‐organic framework (CuBDC‐XN). By precisely engineering electron‐deficient Cu Lewis acid sites and electron‐rich XN‐functionalized Lewis base sites, this bifunctional catalyst enables the synergistic co‐reduction of SO 3 2− and CO 2 into methanesulfonate (MS) at ambient conditions with a Faradaic efficiency of 13.77% (−0.78 V versus RHE). Mechanistic studies reveal that the frustrated Lewis pairs selectively stabilize key intermediates (*CHO and SO 3 2− ) via electrostatic interactions, facilitating nucleophilic attack and C─S coupling with a reduced energy barrier (0.48 eV). In situ spectroscopic analyses and DFT calculations further elucidate the dynamic adsorption‐configuration regulation and intermediate evolution pathway. This work not only establishes a molecular‐level understanding of cooperative Lewis acid‐base catalysis but also provides a universal design principle for the sustainable electrosynthesis of value‐added organosulfur compounds.