FeCo Alloy Clusters Optimized Heterogeneous Catalytic Interface for Driving CO ₂ Hydrogenation to Light Olefins

Abstract The efficient conversion of CO ₂ to light olefins via CO ₂ ‐modified Fischer‐Tropsch synthesis (CO ₂ ‐FTS) with high selectivity and yield remains a critical challenge. Here, the Fe ₃ O ₄ ‐FeCo‐Fe ₅ C ₂ ternary catalyst was successfully constructed. Notably, the different contents of Co doping optimized the heterogeneous catalytic interface of the FeCo alloy clusters, which promoted the targeted conversion of CO ₂ to light olefins in high yield (22.4%) and effectively suppressed the generation of CO (4.4%). The study shows that the formation of FeCo alloy clusters significantly promotes the forward progression of the Reverse Water‐Gas Reaction (RWGS), which can greatly enhance the conversion of CO ₂ and inhibit the formation of CO according to Le Chatelier's principle. Moreover, the FeCo alloy clusters significantly promoted the rapid formation of CH _x and induced the chain growth of CH _x on Fe ₅ C ₂ phase. Hence, the clever construction of FeCo alloy clusters significantly strengthens the kinetic coupling between the RWGS and FTS reactions. Additionally, the in‐situ structural evolution of the catalysts, along with the real‐time formation process of the products, was monitored through in‐situ characterization. This work is promising to provide an effective strategy for CO ₂ hydrogenation to achieve high yields of light olefins over FeCo alloy clusters.