Heteroatom‐Doped Bismuth‐Based Electrocatalysts for CO ₂ Reduction to Formic Acid: Advancement and Perspective

ABSTRACT Electrochemical carbon dioxide reduction reaction (CO 2 RR) represents an electrochemical process that efficiently converts CO 2 into value‐added products, which hold significant environmental and social importance. Bismuth‐based catalysts have emerged as the primary focus in electrocatalytic research for CO 2 conversion into formic acid, owing to their exceptional catalytic performance and selectivity. By strategically doping heterogeneous atoms, the catalytic activity and stability of bismuth‐based catalysts can be significantly improved. However, research in this field is still in its infancy, with relatively few comprehensive review articles available. Herein, we present a comprehensive review of the progress in heteroatom‐doped bismuth‐based catalysts for CO 2 RR toward formic acid production. Initially, this review outlines the market application prospects of bismuth‐based catalysts, the reduction reaction mechanisms, and various modification methods. Furthermore, it systematically summarizes the latest advancements in heteroatom‐doped bismuth‐based catalysts, including non‐metal atom‐doped bismuth (such as S, F, and Te) and metal atom‐doped bismuth (such as Cu, Co, and Sn). Finally, the review explores the future prospects and challenges associated with the development of heterogeneous atom‐doped Bi‐based catalysts. This review provides deeper insights into accelerating the technologies of CO 2 RR to value‐added formic acid formation using Bi‐based catalysts.