Direct cleavage of C=O double bond in CO2 by the subnano MoOx surface on Mo2N

Hao-Xin Liu; Wei-Wei Wang; Xin-Pu Fu; Jin-Cheng Liu; Chun-Jiang Jia

doi:10.1038/s41467-024-53484-y

Direct cleavage of C=O double bond in CO₂ by the subnano MoO_x surface on Mo₂N

Nat Commun. 2024 Oct 23;15(1):9126. doi: 10.1038/s41467-024-53484-y.

Authors

Hao-Xin Liu¹, Wei-Wei Wang², Xin-Pu Fu¹, Jin-Cheng Liu³, Chun-Jiang Jia⁴

Affiliations

¹ Key Laboratory for Colloid and Interface Chemistry, Key Laboratory of Special Aggregated Materials, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P. R. China.
² Key Laboratory for Colloid and Interface Chemistry, Key Laboratory of Special Aggregated Materials, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P. R. China. [email protected].
³ Center for Rare Earth and Inorganic Functional Materials, School of Materials Science and Engineering & National Institute for Advanced Materials, Nankai University, Tianjin, 300350, P. R. China. [email protected].
⁴ Key Laboratory for Colloid and Interface Chemistry, Key Laboratory of Special Aggregated Materials, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P. R. China. [email protected].

Abstract

Compared to H₂-assisted activation mode, the direct dissociation of CO₂ into carbonyl (*CO) with a simplified reaction route is advantageous for CO₂-related synthetic processes and catalyst upgrading, while the stable C = O double bond makes it very challenging. Herein, we construct a subnano MoO₃ layer on the surface of Mo₂N, which provides a dynamically changing surface of MoO₃↔MoO_x (x < 3) for catalyzing CO₂ hydrogenation. Rich oxygen vacancies on the subnano MoO_x surface with a high electron donating capacity served as a scissor to directly shear the C = O double bond of CO₂ to form CO at a high rate. The O atoms leached in CO₂ dissociation are removed timely by H₂ to regenerate active oxygen vacancies. Owing to the greatly enhanced dissociative activation of CO₂, this MoO_x/Mo₂N catalyst without any supported active metals shows excellent performance for catalyzing CO₂ hydrogenation to CO. The construction of highly disordered defective surface on heterostructures paves a new pathway for molecule activation.