High‐Performance Bi‐Based Catalysts for CO₂ Reduction: In Situ Formation of Bi/Bi₂O₂CO₃ and Enhanced Formate Production
Ben Li, Jiadong Chen, Lihua Wang, De Hua Xia, Shanjun Mao, Lingling Xi, Huajie Liu, Sibin Ying, Yong Wang
Abstract
Abstract The unavoidable self‐reduction of Bismuth (Bi)‐based catalysts to zero‐valence Bi often results in detrimental adsorption of OCHO * , leading to unsatisfactory selectivity of HCOOH in the electroreduction of carbon dioxide (CO 2 ). A novel Bi‐tannin (Bi‐TA) complex is developed, which undergoes in situ reconstruction into a Bi/Bi₂O₂CO₃ phase during CO 2 reduction. This reconstructed catalyst exhibits high activity and selectivity, achieving a Faradaic Efficiency (FE) for formate production exceeding 90%, peaking at 96%. Operando spectroscopic and theoretical analyses reveal that the Bi δ+ active site in Bi/Bi₂O₂CO₃ significantly enhances the formation of the OCHO * intermediate, crucial for formate production. The study offers a promising approach to overcoming the limitations of Bi‐based catalysts in CO 2 reduction to formate.