The carburization of transition metal molybdates (MxMoO₄, M= Cu, Ni or Co) and the generation of highly active metal/carbide catalysts for CO₂ hydrogenation

Rodriguez, Jose A.; Xu, Wenqian; Ramirez, Pedro J.; Stachiola, Dario; Brito, Joaquin L.

doi:10.1007/s10562-015-1540-5

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

Journal Article · Wed May 06 00:00:00 EDT 2015 · Catalysis Letters

DOI:https://doi.org/10.1007/s10562-015-1540-5· OSTI ID:1183869

Rodriguez, Jose A. ^[1]; Xu, Wenqian ^[1]; Ramirez, Pedro J. ^[2]; Stachiola, Dario ^[1]; Brito, Joaquin L. ^[3]

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)

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 C_nH₂_n₊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 C_nH₂_n₊₂ (n > 2) hydrocarbons (Co case).

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC00112704

OSTI ID:: 1183869

Report Number(s):: BNL-107990-2015-JA; R&D Project: CO-027; KC0302010

Journal Information:: Catalysis Letters, Vol. 51, Issue 19; ISSN 1011-372X

Publisher:: SpringerCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 40 works

Citation information provided by
Web of Science

References (46)

Synthesis, properties and applications of nanoscale nitrides, borides and carbides Xu, Liqiang; Li, Shouli; Zhang, Yuxu Nanoscale, Vol. 4, Issue 16 https://doi.org/10.1039/c2nr30598d	journal	January 2012
Platinum-Like Behavior of Tungsten Carbide in Surface Catalysis Levy, R. B.; Boudart, M. Science, Vol. 181, Issue 4099 https://doi.org/10.1126/science.181.4099.547	journal	August 1973
Surface Chemistry of Transition Metal Carbides Hwu, Henry H.; Chen, Jingguang G. Chemical Reviews, Vol. 105, Issue 1 https://doi.org/10.1021/cr0204606	journal	January 2005
Metal carbides and nitrides as potential catalysts for hydroprocessing Furimsky, Edward Applied Catalysis A: General, Vol. 240, Issue 1-2 https://doi.org/10.1016/S0926-860X(02)00428-3	journal	February 2003
Preparation and catalytic properties of transition metal carbides and nitrides Oyama, S. T. Catalysis Today, Vol. 15, Issue 2 https://doi.org/10.1016/0920-5861(92)80175-M	journal	June 1992
Push–pull mechanism of hydrodenitrogenation over carbide and sulfide catalysts Schwartz, Viviane; da Silva, Victor Teixeira; Oyama, S. Ted Journal of Molecular Catalysis A: Chemical, Vol. 163, Issue 1-2 https://doi.org/10.1016/S1381-1169(00)00390-3	journal	December 2000
Hydrodesulfurization over supported monometallic, bimetallic and promoted carbide and nitride catalysts Diaz, Brian; Sawhill, Stephanie J.; Bale, Denise H. Catalysis Today, Vol. 86, Issue 1-4 https://doi.org/10.1016/S0920-5861(03)00411-5	journal	November 2003
Synthesis of α-MoC1-x and β-MoCy Catalysts for CO2 Hydrogenation by Thermal Carburization of Mo-oxide in Hydrocarbon and Hydrogen Mixtures Xu, Wenqian; Ramirez, Pedro J.; Stacchiola, Dario Catalysis Letters, Vol. 144, Issue 8 https://doi.org/10.1007/s10562-014-1278-5	journal	June 2014
Production of CO-Free H2 by Formic Acid Decomposition over Mo2C/Carbon Catalysts Koós, Ákos; Solymosi, Frigyes Catalysis Letters, Vol. 138, Issue 1-2 https://doi.org/10.1007/s10562-010-0375-3	journal	June 2010
Phase stabilities and structural relaxations in substoichiometric ${TiC}_{1 - x}$ Hugosson, Håkan W.; Korzhavyi, Pavel; Jansson, Ulf Physical Review B, Vol. 63, Issue 16 https://doi.org/10.1103/PhysRevB.63.165116	journal	April 2001
Superconducting and structural properties of δ-MoC0.681 cubic molybdenum carbide phase Sathish, C. I.; Guo, Yanfeng; Wang, Xia Journal of Solid State Chemistry, Vol. 196 https://doi.org/10.1016/j.jssc.2012.07.037	journal	December 2012
The bending machine: CO ₂ activation and hydrogenation on δ-MoC(001) and β-Mo ₂ C(001) surfaces Posada-Pérez, Sergio; Viñes, Francesc; Ramirez, Pedro J. Phys. Chem. Chem. Phys., Vol. 16, Issue 28 https://doi.org/10.1039/C4CP01943A	journal	January 2014
Effect of the type of precursor and the synthesis method on thiophene hydrodesulfurization activity of activated carbon supported Fe-Mo, Co-Mo and Ni-Mo carbides Puello-Polo, Esneyder; Brito, Joaquín L. Journal of Molecular Catalysis A: Chemical, Vol. 281, Issue 1-2 https://doi.org/10.1016/j.molcata.2007.09.015	journal	February 2008
Effect of interparticle interaction on the low temperature oxidation of CO over size-selected Au nanocatalysts supported on ultrathin TiC films Ono, Luis K.; Roldán-Cuenya, Beatriz Catalysis Letters, Vol. 113, Issue 3-4 https://doi.org/10.1007/s10562-007-9027-7	journal	February 2007
CO ₂ Activation and Methanol Synthesis on Novel Au/TiC and Cu/TiC Catalysts Vidal, Alba B.; Feria, Leticia; Evans, Jaime The Journal of Physical Chemistry Letters, Vol. 3, Issue 16 https://doi.org/10.1021/jz300989e	journal	August 2012
High Activity Carbide Supported Catalysts for Water Gas Shift Schweitzer, Neil M.; Schaidle, Joshua A.; Ezekoye, Obiefune K. Journal of the American Chemical Society, Vol. 133, Issue 8 https://doi.org/10.1021/ja110705a	journal	March 2011
Charge Polarization at a Au-TiC Interface and the Generation of Highly Active and Selective Catalysts for the Low-Temperature Water-Gas Shift Reaction Rodriguez, José A.; Ramírez, Pedro J.; Asara, Gian Giacomo Angewandte Chemie International Edition, Vol. 53, Issue 42 https://doi.org/10.1002/anie.201407208	journal	September 2014
Molybdenum Carbide as Alternative Catalysts to Precious Metals for Highly Selective Reduction of CO ₂ to CO Porosoff, Marc D.; Yang, Xiaofang; Boscoboinik, J. Anibal Angewandte Chemie International Edition, Vol. 53, Issue 26 https://doi.org/10.1002/anie.201404109	journal	May 2014
CO2 hydrogenation on Au/TiC, Cu/TiC, and Ni/TiC catalysts: Production of CO, methanol, and methane Rodriguez, José A.; Evans, Jaime; Feria, Leticia Journal of Catalysis, Vol. 307 https://doi.org/10.1016/j.jcat.2013.07.023	journal	November 2013
Desulfurization of Thiophene on Au/TiC(001): Au−C Interactions and Charge Polarization Rodriguez, José A.; Liu, Ping; Takahashi, Yoshiro Journal of the American Chemical Society, Vol. 131, Issue 24 https://doi.org/10.1021/ja901522a	journal	June 2009
Activation of noble metals on metal-carbide surfaces: novel catalysts for CO oxidation, desulfurization and hydrogenation reactions Rodriguez, José A.; Illas, Francesc Phys. Chem. Chem. Phys., Vol. 14, Issue 2 https://doi.org/10.1039/C1CP22738F	journal	January 2012
Methanol Synthesis and Reverse Water–Gas Shift Kinetics over Cu(110) Model Catalysts: Structural Sensitivity Yoshihara, Jun; Campbell, Charles T. Journal of Catalysis, Vol. 161, Issue 2 https://doi.org/10.1006/jcat.1996.0240	journal	July 1996
CO2 Hydrogenation over Carbide Catalysts. Dubois, Jean-Luc; Sayama, Kazuhiro; Arakawa, Hironori Chemistry Letters, Issue 1 https://doi.org/10.1246/cl.1992.5	journal	January 1992
In situ time-resolved X-ray diffraction study of the synthesis of Mo ₂ C with different carburization agents Guzmán, Héctor J.; Xu, Wenqian; Stacchiola, Dario Canadian Journal of Chemistry, Vol. 91, Issue 7 https://doi.org/10.1139/cjc-2012-0516	journal	July 2013
Effect of Phase Composition of the Oxidic Precursor on the HDS Activity of the Sulfided Molybdates of Fe(II), Co(II), and Ni(II) Brito, Joaquı́n L.; Barbosa, A. Liliana Journal of Catalysis, Vol. 171, Issue 2 https://doi.org/10.1006/jcat.1997.1796	journal	October 1997
Electronic Properties and Phase Transformations in CoMoO ₄ and NiMoO ₄ : XANES and Time-Resolved Synchrotron XRD Studies Rodriguez, José A.; Chaturvedi, Sanjay; Hanson, Jonathan C. The Journal of Physical Chemistry B, Vol. 102, Issue 8 https://doi.org/10.1021/jp972137q	journal	February 1998
Nickel molybdate as precursor of HDS catalysts: Effect of phase composition Brito, Joaqu�n L.; Barbosa, A. Liliana; Albornoz, Alberto Catalysis Letters, Vol. 26, Issue 3-4 https://doi.org/10.1007/BF00810606	journal	January 1994
Two-dimensional detector software: From real detector to idealised image or two-theta scan Hammersley, A. P.; Svensson, S. O.; Hanfland, M. High Pressure Research, Vol. 14, Issue 4-6, p. 235-248 https://doi.org/10.1080/08957959608201408	journal	January 1996
Reaction of H ₂ and H ₂ S with CoMoO ₄ and NiMoO ₄ : TPR, XANES, Time-Resolved XRD, and Molecular-Orbital Studies Rodriguez, José A.; Chaturvedi, Sanjay; Hanson, Jonathan C. The Journal of Physical Chemistry B, Vol. 103, Issue 5 https://doi.org/10.1021/jp983115m	journal	February 1999
On the role of hydrogen during the reduction–carburation of MoO3 into molybdenum oxycarbide Bouchy, Christophe; Pham-huu, Cuong; Ledoux, Marc J. Journal of Molecular Catalysis A: Chemical, Vol. 162, Issue 1-2 https://doi.org/10.1016/S1381-1169(00)00300-9	journal	November 2000
A new route to the metastable FCC molybdenum carbide α-MoC1−x Bouchy, Christophe; Derouane-Abd Hamid, Sharifah Bee; Derouane, Eric G. Chemical Communications, Issue 2 https://doi.org/10.1039/a907534h	journal	January 2000
Activated carbon supported bimetallic CoMo carbides synthesized by carbothermal hydrogen reduction Liang, Changhai; Ma, Wenping; Feng, Zhaochi Carbon, Vol. 41, Issue 9 https://doi.org/10.1016/S0008-6223(03)00169-6	journal	January 2003
Hydrogen Adsorption Structures and Energetics on Iron Surfaces at High Coverage Wang, Tao; Wang, Shengguang; Luo, Qiquan The Journal of Physical Chemistry C, Vol. 118, Issue 8 https://doi.org/10.1021/jp410635z	journal	February 2014
Methanol Synthesis Waugh, K. C. Catalysis Today, Vol. 15, Issue 1 https://doi.org/10.1016/0920-5861(92)80122-4	journal	May 1992
Mechanism of methanol synthesis from CO2/CO/H2 mixtures over copper/zinc oxide/alumina catalysts: use of14C-labelled reactants Chinchen, G. C.; Denny, P. J.; Parker, D. G. Applied Catalysis, Vol. 30, Issue 2 https://doi.org/10.1016/S0166-9834(00)84123-8	journal	April 1987
Fundamental studies of methanol synthesis from CO2 hydrogenation on Cu(111), Cu clusters, and Cu/ZnO(0001̄) Yang, Yixiong; Evans, Jaime; Rodriguez, Jose A. Physical Chemistry Chemical Physics, Vol. 12, Issue 33 https://doi.org/10.1039/c001484b	journal	January 2010
Methanol synthesis on Cu(100) from a binary gas mixture of CO2 and H2 Rasmussen, P. B.; Holmblad, P. M.; Askgaard, T. Catalysis Letters, Vol. 26, Issue 3-4 https://doi.org/10.1007/BF00810611	journal	January 1994
Synthesis of methanol from a mixture of H2 and CO2 on Cu(100) Rasmussen, P. B.; Kazuta, M.; Chorkendorff, I. Surface Science, Vol. 318, Issue 3 https://doi.org/10.1016/0039-6028(94)90101-5	journal	October 1994
Does CO ₂ dissociatively adsorb on Cu surfaces? Nakamura, J.; Rodriguez, J. A.; Campbell, C. T. Journal of Physics: Condensed Matter, Vol. 1, Issue SB https://doi.org/10.1088/0953-8984/1/SB/026	journal	October 1989
Interaction of carbon dioxide with clean and oxygenated Cu(110) surfaces Schneider, T.; Hirschwald, W. Catalysis Letters, Vol. 14, Issue 2 https://doi.org/10.1007/BF00765233	journal	January 1992
Methanation of carbon dioxide on nickel(100) and the effects of surface modifiers Peebles, D. E.; Goodman, D. W.; White, J. M. The Journal of Physical Chemistry, Vol. 87, Issue 22 https://doi.org/10.1021/j100245a014	journal	October 1983
Carbon Dioxide Hydrogenation on Ni(110) Vesselli, Erik; De Rogatis, Loredana; Ding, Xunlei Journal of the American Chemical Society, Vol. 130, Issue 34 https://doi.org/10.1021/ja802554g	journal	July 2008
Methane formation from the hydrogenation of carbon dioxide on Ni(110) surface – a density functional theoretical study Bothra, Pallavi; Periyasamy, Ganga; Pati, Swapan K. Physical Chemistry Chemical Physics, Vol. 15, Issue 15 https://doi.org/10.1039/c3cp44495c	journal	January 2013
CO2 activation and reaction with hydrogen on Ni(110): formate formation Wambach, J.; Illing, G.; Freund, H. -J. Chemical Physics Letters, Vol. 184, Issue 1-3 https://doi.org/10.1016/0009-2614(91)87194-G	journal	September 1991
A Cobalt-Based Catalyst for the Hydrogenation of CO ₂ under Ambient Conditions Jeletic, Matthew S.; Mock, Michael T.; Appel, Aaron M. Journal of the American Chemical Society, Vol. 135, Issue 31 https://doi.org/10.1021/ja406601v	journal	July 2013
The effect of CO2 on a cobalt-based catalyst for low temperature Fischer–Tropsch synthesis Yao, Y.; Liu, X.; Hildebrandt, D. Chemical Engineering Journal, Vol. 193-194 https://doi.org/10.1016/j.cej.2012.04.045	journal	June 2012

Cited By (3)

Potassium-Promoted Molybdenum Carbide as a Highly Active and Selective Catalyst for CO ₂ Conversion to CO Porosoff, Marc D.; Baldwin, Jeffrey W.; Peng, Xi ChemSusChem, Vol. 10, Issue 11 https://doi.org/10.1002/cssc.201700412	journal	May 2017
Activation of CO ₂ , CS ₂ , and Dehydrogenation of Formic Acid Catalyzed by Iron(II) Hydride Complexes : Activation of CO Wang, Lin; Sun, Hongjian; Zuo, Zhenyu European Journal of Inorganic Chemistry, Vol. 2016, Issue 33 https://doi.org/10.1002/ejic.201600642	journal	October 2016
Cu-Mo2C/MCM-41: An Efficient Catalyst for the Selective Synthesis of Methanol from CO2 Liu, Xiaoran; Song, Yingquan; Geng, Wenhao Catalysts, Vol. 6, Issue 5 https://doi.org/10.3390/catal6050075	journal	May 2016

Similar Records

Simple molybdate selective oxidation catalysts containing excess MoO/sub 3/ for C/sub 4/ hydrocarbon oxidation to maleic anhydride

Technical Report · Tue Jan 01 00:00:00 EST 1985 · OSTI ID:1183869

Ozkan, U S

Reaction of H{sub 2} and H{sub 2}S with CoMoO{sub 4} and NiMoO{sub 4}: TPR, XANES, time-resolved XRD, and molecular-orbital studies

Journal Article · Thu Feb 04 00:00:00 EST 1999 · Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical · OSTI ID:1183869

Rodriguez, J A; Chaturvedi, S; Hanson, J C; +1 more

Phase transformations and electronic properties in mixed-metal oxides: Experimental and theoretical studies on the behavior of NiMoO{sub 4} and MgMoO{sub 4}

Journal Article · Sat Jan 08 00:00:00 EST 2000 · Journal of Chemical Physics · OSTI ID:1183869

Rodriguez, Jose A; Hanson, Jonathan C; Chaturvedi, Sanjay; +2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
molybdenum carbide
molybdenum oxide
molybdate
nickel
copper
cobalt
CO₂ hydrogenation

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

Citation Formats

References (46)

Cited By (3)

Similar Records

Related Subjects