Steering the Site Distance of Atomic Cu−Cu Pairs by First‐Shell Halogen Coordination Boosts CO 2 ‐to‐C 2 Selectivity

作者：Fengya Ma, Pengfang Zhang, Xiaobo Zheng, Liang Chen, Yunrui Li, Zechao Zhuang, Yameng Fan, Peng Jiang, Hui Zhao, Jiawei Zhang, Yuming Dong, Yongfa Zhu, Dingsheng Wang, Yao Wang · 发表于：Angewandte Chemie · 年份：2024 · DOI：10.1002/ange.202412785 · 被引用次数：12 · 研究领域：CO2 Reduction Techniques and Catalysts、Metal-Organic Frameworks: Synthesis and Applications、Ionic liquids properties and applications

Abstract Electrocatalytic reduction of CO 2 into C 2 products of high economic value provides a promising strategy to realize resourceful CO 2 utilization. Rational design and construct dual sites to realize the CO protonation and C−C coupling to unravel their structure‐performance correlation is of great significance in catalysing electrochemical CO 2 reduction reactions. Herein, Cu−Cu dual sites with different site distance coordinated by halogen at the first‐shell are constructed and shows a higher intramolecular electron redispersion and coordination symmetry configurations. The long‐range Cu−Cu (Cu−I−Cu) dual sites show an enhanced Faraday efficiency of C 2 products, up to 74.1 %, and excellent stability. In addition, the linear relationships that the long‐range Cu−Cu dual sites are accelerated to C 2 H 4 generation and short‐range Cu−Cu (Cu−Cl−Cu) dual sites are beneficial for C 2 H 5 OH formation are disclosed. In situ electrochemical attenuated total reflection surface enhanced infrared absorption spectroscopy, in situ Raman and theoretical calculations manifest that long‐range Cu−Cu dual sites can weaken reaction energy barriers of CO hydrogenation and C−C coupling, as well as accelerating deoxygenation of *CH 2 CHO. This study uncovers the exploitation of site‐distance‐dependent electrochemical properties to steer the CO 2 reduction pathway, as well as a potential generic tactic to target C 2 synthesis by constructing the desired Cu−Cu dual sites.