Cobalt-modified molybdenum carbide as a selective catalyst for hydrodeoxygenation of furfural

Lin, Zhexi; Wan, Weiming; Yao, Siyu; Chen, Jingguang G.

doi:10.1016/j.apcatb.2018.03.113

Cobalt-modified molybdenum carbide as a selective catalyst for hydrodeoxygenation of furfural

Journal Article · Tue Apr 03 00:00:00 EDT 2018 · Applied Catalysis B: Environmental

DOI:https://doi.org/10.1016/j.apcatb.2018.03.113· OSTI ID:1462482

Lin, Zhexi ^[1]; Wan, Weiming ^[1]; Yao, Siyu ^[2]; ^[3]

Columbia Univ., New York, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Columbia Univ., New York, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)

The hydrodeoxygenation (HDO) reaction is crucial to the upgrading of biomass-derived furfural to produce a promising fuel additive, 2-methylfuran. In order to enhance the stability of the molybdenum carbide (Mo₂C) catalyst, this work utilizes cobalt (Co) modification to tune the oxygen and furfural binding energies on Mo₂C. Density functional theory (DFT) calculations of the adsorption configuration of furfural on Mo₂C(0001) and cobalt-modified molybdenum carbide (Co/Mo₂C(0001)) reveal that the C=O bond of furfural is elongated, facilitating the selective C=O scission to produce 2-methylfuran. The reduced oxygen and furfural binding energies on Co/Mo₂C(0001) allow the facile removal of surface oxygen and furfural to improve the stability of the catalyst. Temperature-programmed desorption (TPD) experiments on model surfaces confirm the enhanced stability and overall HDO performance of Co/Mo₂C/Mo(110). Based on the results from high-resolution electron energy loss spectroscopy (HREELS), 2-methylfuran-like intermediates are observed on both Mo₂C/Mo(110) and Co/Mo₂C/Mo(110). Parallel reactor evaluations over the corresponding powder catalysts further demonstrate the enhanced stability of Co/Mo₂C over Mo₂C at ambient pressure. Furthermore, this work illustrates the important roles of oxygen and furfural binding energies in the furfural HDO reaction on both model surfaces and powder catalysts, which in turn provides insights into designing selective and stable carbide-based catalysts for HDO reactions.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231; SC0012704

OSTI ID:: 1462482

Alternate ID(s):: OSTI ID: 1703716

Report Number(s):: BNL--207917-2018-JAAM

Journal Information:: Applied Catalysis B: Environmental, Journal Name: Applied Catalysis B: Environmental Journal Issue: C Vol. 233; ISSN 0926-3373

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Catalyst-free synthesis of biodiesel precursors from biomass-based furfuryl alcohols in the presence of H ₂ O and air Qin, Shengxiang; Li, Teng; Zhang, Man Green Chemistry, Vol. 21, Issue 23 https://doi.org/10.1039/c9gc03179k	journal	January 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Biomass
Carbides
Density functional theory calculations
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Cobalt-modified molybdenum carbide as a selective catalyst for hydrodeoxygenation of furfural

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