Fluorine‐Tuned Atomically Dispersed Magnesium Sites for Highly Efficient CO 2 Electrocatalytic Reduction

作者：Huanyan Liu, Mingxin Gao, Weidong Cheng, Zhongnan Ling, Shuming Zhou, Sangseok Yu, Jiankang Liu, Zhongjun Chen, Guang Mo, Xuehui Wu, Zhonghua Wu, Yaguang Peng, Xinchen Kang, Buxing Han, Xueqing Xing · 发表于：Advanced Functional Materials · 年份：2025 · DOI：10.1002/adfm.202521705 · 被引用次数：3 · 研究领域：CO2 Reduction Techniques and Catalysts、Carbon dioxide utilization in catalysis、Catalysts for Methane Reforming

Abstract The electrochemical carbon dioxide reduction reaction (CO 2 RR) represents a promising strategy for converting CO 2 into CO. Atomically dispersed transition metal sites have an exceptional ability to activate CO 2 . However, the strong hybridization between the 3 d orbitals of these transition metals and the 5σ or 2π * orbital of CO significantly impedes * CO desorption, thereby limiting the overall CO generation activity. In contrast, s ‐block metals, with diffuse 3 s electron clouds, exhibit weaker interactions with * CO. Nevertheless, their practical application is hindered by the high energy barrier associated with the formation of the * COOH intermediate. To address these challenges, a fluorine(F)‐tuned magnesium single‐atom catalyst (Mg‐SAC) is developed. Remarkably, this catalyst achieved a CO Faraday efficiency of 97.3% and a current density of 260.4 mA cm −2 at −0.4 V vs the reversible hydrogen electrode in a flow cell, surpassing the performance of most state‐of‐the‐art SACs and transition metal catalysts reported in the literature. Mechanistic studies reveal that * CO desorption on Mg sites is significantly easier compared to that on Fe and Co sites. Furthermore, the incorporation of F atoms modifies the electronic structure of the MgN 4 sites, substantially lowering the energy barrier for the formation of the critical * COOH intermediate.