N/O Co‐Coordinated Cu Active Sites in Metal–Organic Framework for the Electrochemical Reduction CO 2 to C 2+ Products
Jian‐Feng Lu, Shan Zou, Zi‐Yan Chen, Zi‐Hao Zhu, Jian Zhao, Sheng‐Li Hou, Hui Xu, Sui‐Jun Liu, He‐Rui WenABSTRACT
Metal‐organic frameworks (MOFs) are promising candidates for catalyzing the electrochemical CO 2 reduction reaction (CO 2 RR) to alleviate environmental and energy issues. However, rationally designing active sites to enhance the adsorption of the key *CO intermediate for efficient CO 2 ‐to‐C 2+ conversion remains a significant challenge. Herein, we propose a coordination atom regulating strategy to optimize the electronic structure of the Cu site for CO 2 RR. A Cu‐MOF ( JXUST‐304 ) featuring CuN 2 O 2 active site (originating from CuN 2 O 3 nodes removed of coordinated DMF) was constructed based on a ligand incorporating both pyridine N and ‐COOH groups. JXUST‐304 displays superior catalytic performance in the CO 2 ‐to‐C 2+ conversion with a Faraday efficiency of 64.7% alongside a partial current density of 129.1 mA cm −2 , surpassing similar Cu‐MOF with CuN 4 active sites. The unique N/O co‐coordination mode modulates the electronic structure to optimize the d‐band center of Cu sites, which enhances the adsorption of *CO intermediate. Meanwhile, 3d xz ‐2p z π back bonding interaction reduces the formation energy barrier for *CHO to facilitate C–C coupling, resulting in a selective increase in C 2+ products. This work offers insight into regulating the catalytic active sites within MOFs at the molecular level to promote the generation of targeted products.