The carburization of transition metal molybdates (MxMoO₄, M= Cu, Ni or Co) and the generation of highly active metal/carbide catalysts for CO₂ hydrogenation
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, a-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).
- Authors:
-
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States); Univ. Central De Venezuela, Caracas (Venesuela)
- Inst. Venezolano de Investigaciones Cientificas, Caracas (Venezuela)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1183869
- Report Number(s):
- BNL-107990-2015-JA
Journal ID: ISSN 1011-372X; R&D Project: CO-027; KC0302010
- Grant/Contract Number:
- SC00112704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Catalysis Letters
- Additional Journal Information:
- Journal Volume: 51; Journal Issue: 19; Journal ID: ISSN 1011-372X
- Publisher:
- Springer
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; molybdenum carbide; molybdenum oxide; molybdate; nickel; copper; cobalt; CO₂ hydrogenation
Citation Formats
Rodriguez, Jose A., Xu, Wenqian, Ramirez, Pedro J., Stachiola, Dario, and Brito, Joaquin L. The carburization of transition metal molybdates (MxMoO₄, M= Cu, Ni or Co) and the generation of highly active metal/carbide catalysts for CO₂ hydrogenation. United States: N. p., 2015.
Web. doi:10.1007/s10562-015-1540-5.
Rodriguez, Jose A., Xu, Wenqian, Ramirez, Pedro J., Stachiola, Dario, & Brito, Joaquin L. The carburization of transition metal molybdates (MxMoO₄, M= Cu, Ni or Co) and the generation of highly active metal/carbide catalysts for CO₂ hydrogenation. United States. https://doi.org/10.1007/s10562-015-1540-5
Rodriguez, Jose A., Xu, Wenqian, Ramirez, Pedro J., Stachiola, Dario, and Brito, Joaquin L. Wed .
"The carburization of transition metal molybdates (MxMoO₄, M= Cu, Ni or Co) and the generation of highly active metal/carbide catalysts for CO₂ hydrogenation". United States. https://doi.org/10.1007/s10562-015-1540-5. https://www.osti.gov/servlets/purl/1183869.
@article{osti_1183869,
title = {The carburization of transition metal molybdates (MxMoO₄, M= Cu, Ni or Co) and the generation of highly active metal/carbide catalysts for CO₂ hydrogenation},
author = {Rodriguez, Jose A. and Xu, Wenqian and Ramirez, Pedro J. and Stachiola, Dario and Brito, Joaquin L.},
abstractNote = {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, a-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).},
doi = {10.1007/s10562-015-1540-5},
journal = {Catalysis Letters},
number = 19,
volume = 51,
place = {United States},
year = {Wed May 06 00:00:00 EDT 2015},
month = {Wed May 06 00:00:00 EDT 2015}
}
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