BCN‐Supported CoFe Alloy Catalysts for Enhanced C─C Coupling in Photothermocatalytic CO Hydrogenation

Abstract The high selectivity of C─C coupling reactions in Fischer–Tropsch synthesis (FTS) is often limited due to the difficulty in the regulation of transition metals acting as active sites to balance between C─C chain propagation and over hydrogenation. Herein, BCN‐supported CoFe alloy catalyst has been successfully constructed for promoting C─C chain propagation. When exposed to light irradiation, the CoFe‐BCN catalyst exhibits a higher CO conversion of 18.4% with the enhanced selectivity toward multi‐carbon (C 2+ ) hydrocarbons that increases from 22.4% to 64.1%, and the reduced over hydrogenation to CH 4 that decreases from 74.8% to 25.4% in contrast to Co‐BCN catalyst. Structural characterizations indicate that introducing Fe to create CoFe alloy can decrease the d‐band center of Co, which significantly promotes C─C coupling reactions but weakens hydrogenation in FTS process. The findings underscore the potential of modifying catalysts with metal atoms to optimize their electronic structure to regulate reaction pathways in CO hydrogenation for high‐value products formation.