Integrated “Two‐in‐One” Strategy for High‐Rate Electrocatalytic CO2 Reduction to Formate

• Published in: Angewandte Chemie International Edition 2025-01, Vol.64 (3), p.e202415726-n/a
• Main Authors: Lei, Peng‐Xia, Liu, Shao‐Qing, Wen, Qi‐Rui, Wu, Jia‐Yi, Wu, Shuwen, Wei, Xiaoxiao, Feng, Renfei, Fu, Xian‐Zhu, Luo, Jing‐Li
• Format: Article
• Language: English
• Subjects: Adsorption; Carbon dioxide; Chemical reduction; CO2 adsorption; Current density; Defects; Electrochemical CO2 reduction; Electrochemistry; Formate; Protonation; Water dissociation
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202415726

The electrochemical CO2 reduction reaction (ECR) is a promising pathway to producing valuable chemicals and fuels. Despite extensive studies reported, improving CO2 adsorption for local CO2 enrichment or water dissociation to generate sufficient H* is still not enough to achieve industrial‐relevant current densities. Herein, we report a “two‐in‐one” catalyst, defective Bi nanosheets modified by CrOx (Bi−CrOx), to simultaneously promote CO2 adsorption and water dissociation, thereby enhancing the activity and selectivity of ECR to formate. The Bi−CrOx exhibits an excellent Faradaic efficiency (≈100 %) in a wide potential range from −0.4 to −0.9 V. In addition, it achieves a remarkable formate partial current density of 687 mA cm−2 at a moderate potential of −0.9 V without iR compensation, the highest value at −0.9 V reported so far. Control experiments and theoretical simulations revealed that the defective Bi facilitates CO2 adsorption/activation while the CrOx accounts for enhancing the protonation process via accelerating H2O dissociation. This work presents a pathway to boosting formate production through tuning CO2 and H2O species at the same time. A “two‐in‐one” catalyst, defective Bi modified by CrOx was developed for high‐rate formate electrosynthesis through CO2 reduction. The defective Bi provides abundant active sites for CO2 adsorption, and the CrOx species promote the hydrogenation of CO2* to *OCHO by accelerating H2O dissociation to provide H*, which synergistically contributes to the high performance.