Stabilizing Co₂C with H₂O and K promoter for CO₂ hydrogenation to C₂₊ hydrocarbons

The decomposition of cobalt carbide (Co₂C) to metallic cobalt in CO₂ hydrogenation results in a notable drop in the selectivity of valued C₂₊ products, and the stabilization of Co₂C remains a grand challenge. Here, we report an in situ synthesized K-Co₂C catalyst, and the selectivity of C₂₊ hydrocarbons in CO₂ hydrogenation achieves 67.3% at 300°C, 3.0 MPa. Experimental and theoretical results elucidate that CoO transforms to Co₂C in the reaction, while the stabilization of Co₂C is dependent on the reaction atmosphere and the K promoter. During the carburization, the K promoter and H₂O jointly assist in the formation of surface C^* species via the carboxylate intermediate, while the adsorption of C^* on CoO is enhanced by the K promoter. The lifetime of the K-Co₂C is further prolonged from 35 hours to over 200 hours by co-feeding H₂O. This work provides a fundamental understanding toward the role of H₂O in Co₂C chemistry, as well as the potential of extending its application in other reactions.