Engineering the Cu(0)–Co <sub>2</sub> C Interface via Reaction-Induced Reconstruction for CO <sub>2</sub> Hydrogenation to C <sub>2+</sub> Hydrocarbons
Mingrui Wang, Shendong Guo, Siyang Yan, Zhiqun Wang, Guanghui Zhang, Hui Gao, Miao Zhang, Kai Bian, Jiaxu Liu, Xiaowa Nie, Jianrong Zeng, Chunshan Song, Xinwen Guo
Abstract
High Resolution Image Download MS PowerPoint Slide 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.