Promoting asymmetric OC-COH coupling on bipyridine-modified copper catalyst for CO2 electroreduction into C2+ products

2, 2′-bipyridine-modified copper realizes CO 2 electroreduction to C 2+ products. • Excellent performance with a maximum C 2+ Faradaic efficiency of 70%. • Asymmetric catalytic sites promote OC-COH coupling, driving C 2+ production. Electrochemical reduction of CO 2 to value-added multi‑carbon (C 2+ ) products represents a promising technology for sustainable chemical synthesis and environmental remediation. However, achieving highly efficient CO 2 electroreduction toward C 2+ products remains challenging due to the high energy barriers inherent to carbon‑carbon (C C) coupling. Herein, we report a 2, 2′-bipyridine-modified copper catalyst with asymmetric catalytic sites (bipyridine-modified Cu sites and adjacent bare Cu sites), which exhibits exceptional selectivity with low overpotential for CO 2 electroreduction to C 2+ products. The catalyst achieves a maximum C 2+ Faradaic efficiency of 70% at −0.64 V vs. RHE in a gas-diffusion flow cell, significantly enhanced compared with copper catalyst without 2, 2′-bipyridine (51%). Mechanistic investigations reveal that the copper sites modified by 2, 2′-bipyridine facilitate the formation of *COH intermediate, while adjacent bare copper sites realize *CO formation. Furthermore, the asymmetric catalytic sites promote OC-COH coupling, thereby overcoming the high energy barrier inherent to C C coupling and effectively driving C 2+ production. Our work establishes asymmetric catalytic sites engineering as a strategic paradigm for advancing CO 2 -to-C 2+ conversion catalysts. A 2, 2′-bipyridine-modified copper catalyst enables asymmetric C C coupling between *CO and *COH intermediates, achieving efficient CO 2 -to-C 2+ conversion. Download: Download high-res image (116KB) Download: Download full-size image