Engineering the Cu(0)–Co ₂ C Interface via Reaction-Induced Reconstruction for CO ₂ Hydrogenation to C ₂₊ Hydrocarbons

Interfacial catalysts show considerable potential for the synthesis of multicarbon products from CO 2 hydrogenation by leveraging synergistic effects in C═O bond activation and C–C coupling. However, controllably constructing such interfaces under operational conditions remains highly challenging. Here, we engineer a Cu(0)–Co 2 C interfacial architecture through a reaction-induced reconstruction strategy. During CO 2 hydrogenation, Co–Cu oxides are initially reduced to metallic Co(0) and Cu(0), with the K promoter unsealing the in situ carburization of Co(0) to form Co 2 C. An outside-in carburization mechanism is elucidated and can be manipulated by tailoring the Co(0)–Cu(0) interaction. Compared to Co(0)–Cu(0) bimetals, the optimized Cu(0)-Co 2 C interfacial catalyst achieves a remarkable leap in C 2+ hydrocarbon selectivity from ∼1% to ∼60% while maintaining robust catalytic activity. It delivers a record C 2+ yield of 19.4 mmol g –1 Co2C h –1 at 300 °C and 3 MPa, outperforming the K–Co 2 C reference catalyst by a factor of 2.5. The Cu(0)–Co 2 C interface primarily promotes the CO*-mediated reaction pathways and effectively enhances CH 2 * coupling. Our findings systematically unravel the dynamic reconstruction mechanisms and interfacial synergy in Co–Cu catalysts, establishing a rational methodology for designing in situ -evolved metal-carbide interfaces to advance CO 2 valorization technologies.