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The Carburization of Transition Metal Molybdates (MxMoO4, M = Cu, Ni or Co) and the Generation of Highly Active Metal/Carbide Catalysts for CO2 Hydrogenation

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Abstract

A new approach has been tested for the preparation of metal/Mo2C catalysts using mixed-metal oxide molybdates as precursors. Synchrotron-based in situ time-resolved X-ray diffraction was used to study the reduction and carburization processes of Cu3(MoO4)2(OH)2, α-NiMoO4 and CoMoO4·nH2O by thermal treatment under mixtures of hydrogen and methane. In all cases, the final product was β-Mo2C and a metal phase (Cu, Ni, or Co), but the transition sequence varied with the different metals, and it could be related to the reduction potential of the Cu2+, Ni2+ and Co2+ cations inside each molybdate. The synthesized Cu/Mo2C, Ni/Mo2C and Co/Mo2C catalysts were highly active for the hydrogenation of CO2. The metal/Mo2C systems exhibited large variations in the selectivity towards methanol, methane and CnH2n+2 (n > 2) hydrocarbons depending on the nature of the supported metal and its ability to cleave C–O bonds. Cu/Mo2C displayed a high selectivity for CO and methanol production. Ni/Mo2C and Co/Mo2C were the most active catalysts for the activation and full decomposition of CO2, showing high selectivity for the production of methane (Ni case) and CnH2n+2 (n > 2) hydrocarbons (Co case).

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Acknowledgments

The research carried out at BNL was supported by the U.S. Department of Energy, Chemical Sciences Division (DE-AC02-98CH10886). P.J.R. is grateful to INTEVEP and IDB for support of the work carried out at UCV.

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Authors and Affiliations

  1. Chemistry Department, Brookhaven National Laboratory, Upton, NY, 11973, USA

    Wenqian Xu, Pedro J. Ramírez, Dario Stacchiola & José A. Rodriguez

  2. Facultad de Ciencias, Universidad Central de Venezuela, Apartado 20513, Caracas, 1020-A, Venezuela

    Pedro J. Ramírez

  3. Centro de Química, Instituto Venezolano de Investigaciones Científicas (IVIC), Apartado 21827, Caracas, 1020-A, Venezuela

    Joaquín L. Brito

Authors
  1. Wenqian Xu
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  2. Pedro J. Ramírez
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  3. Dario Stacchiola
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  4. Joaquín L. Brito
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  5. José A. Rodriguez
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Correspondence to José A. Rodriguez.

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Xu, W., Ramírez, P.J., Stacchiola, D. et al. The Carburization of Transition Metal Molybdates (MxMoO4, M = Cu, Ni or Co) and the Generation of Highly Active Metal/Carbide Catalysts for CO2 Hydrogenation. Catal Lett 145, 1365–1373 (2015). https://doi.org/10.1007/s10562-015-1540-5

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  • DOI: https://doi.org/10.1007/s10562-015-1540-5

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