Designing mesh-like defective molybdenum carbides for ethanol synthesis via syngas-derived DMO hydrogenation

doi:10.1016/S1872-2067(25)64713-9

Abstract

Abstract:

Molybdenum carbide has shown great potential in various hydrogenation reactions, and serves as a primary active species for synthesis of ethanol from dimethyl oxalate hydrogenation process which is a crucial step in the efficient utilization of coal resources. In this study, a molybdenum carbide catalyst with a three-dimensional mesh-like hollow structure and lattice defects was carefully designed. The MoO₃ precursor with abundant oxygen vacancies and defects was prepared by flame spray pyrolysis, and a structural modifier, Cu, was introduced by sputtering. The Cu deposited by sputtering affected the carburization and phase evolution processes. A three-dimensional mesh-like hollow structure composed of defective molybdenum carbide is formed, with the β-Mo₂C exhibiting lattice distortions and defects. This defective β-Mo₂C exhibits high reactivity, and facilitates the C=O hydrogenation process, showing a high reactivity of 83.1% yield in the hydrogenation of dimethyl oxalate. This work provides a new approach to the design and application of molybdenum carbide catalysts.

Key words: Syngas, Dimethyl oxalate Hydrogenation, Ethanol, Molybdenum carbides

Yannan Sun, Jiafeng Yu, Xingtao Sun, Yu Han, Qingjie Ge, Jian Sun. Designing mesh-like defective molybdenum carbides for ethanol synthesis via syngas-derived DMO hydrogenation[J]. Chinese Journal of Catalysis, 2025, 73: 234-241.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64713-9

https://www.cjcatal.com/EN/Y2025/V73/I6/234

Figures/Tables 7

Fig. 1. The catalytic performance of different Mo-based catalysts. Reaction conditions: T = 230 °C, H2/DMO = 120, p = 3.0 MPa, LHSV = 0.3 h-1 (*SP-Cu/FSP-MoO3 at a LHSV = 0.15 h-1).

Fig. 2. The TEM images of spent catalysts. (a) The comm-MoO3 catalyst; (b) The FSP-MoO3 catalyst; (c) The IM-Cu/FSP-MoO3 catalyst.

Fig. 3. The TEM images of the spent SP-Cu/FSP-MoO3 catalyst.

Fig. 4. XRD patterns of the fresh (a), carburized (b), and spent (c) catalysts and the standard JCPDF cards.

Fig. 5. Rietveld XRD patterns of the carburized samples of IM-Cu/FSPMoO3 and SP-Cu/FSP-MoO3 catalysts and the structure of β-Mo2C from the Rietveld XRD results.

Fig. 6. Neutron diffraction patterns of carburized and spent samples of the SP-Cu/FSP-MoO3 catalyst and the models of β-Mo2C according to the corresponding fittings.

Fig. 7. (a) Rietveld XRD patterns of the spent samples of SP-Cu/FSP-MoO3 catalysts with different sputtering time. (b) The structure of β-Mo2C from the Rietveld XRD results.

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