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

Abstract

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-basedmore » catalysts for HDO reactions.« less

Authors:
 [1];  [1];  [2]; ORCiD logo [3]
  1. Columbia Univ., New York, NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Columbia Univ., New York, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
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:
1462482
Alternate Identifier(s):
OSTI ID: 1703716
Report Number(s):
BNL-207917-2018-JAAM
Journal ID: ISSN 0926-3373
Grant/Contract Number:  
SC0012704; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Applied Catalysis B: Environmental
Additional Journal Information:
Journal Volume: 233; Journal Issue: C; Journal ID: ISSN 0926-3373
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; Biomass; Hydrodeoxygenation; Heterogeneous catalysis; Density functional theory calculations; Carbides

Citation Formats

Lin, Zhexi, Wan, Weiming, Yao, Siyu, and Chen, Jingguang G. Cobalt-modified molybdenum carbide as a selective catalyst for hydrodeoxygenation of furfural. United States: N. p., 2018. Web. doi:10.1016/j.apcatb.2018.03.113.
Lin, Zhexi, Wan, Weiming, Yao, Siyu, & Chen, Jingguang G. Cobalt-modified molybdenum carbide as a selective catalyst for hydrodeoxygenation of furfural. United States. https://doi.org/10.1016/j.apcatb.2018.03.113
Lin, Zhexi, Wan, Weiming, Yao, Siyu, and Chen, Jingguang G. Tue . "Cobalt-modified molybdenum carbide as a selective catalyst for hydrodeoxygenation of furfural". United States. https://doi.org/10.1016/j.apcatb.2018.03.113. https://www.osti.gov/servlets/purl/1462482.
@article{osti_1462482,
title = {Cobalt-modified molybdenum carbide as a selective catalyst for hydrodeoxygenation of furfural},
author = {Lin, Zhexi and Wan, Weiming and Yao, Siyu and Chen, Jingguang G.},
abstractNote = {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.},
doi = {10.1016/j.apcatb.2018.03.113},
journal = {Applied Catalysis B: Environmental},
number = C,
volume = 233,
place = {United States},
year = {Tue Apr 03 00:00:00 EDT 2018},
month = {Tue Apr 03 00:00:00 EDT 2018}
}

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Works referenced in this record:

Liquid-Phase Catalytic Processing of Biomass-Derived Oxygenated Hydrocarbons to Fuels and Chemicals
journal, September 2007

  • Chheda, Juben N.; Huber, George W.; Dumesic, James A.
  • Angewandte Chemie International Edition, Vol. 46, Issue 38, p. 7164-7183
  • DOI: 10.1002/anie.200604274

Synergies between Bio- and Oil Refineries for the Production of Fuels from Biomass
journal, September 2007

  • Huber, George W.; Corma, Avelino
  • Angewandte Chemie International Edition, Vol. 46, Issue 38, p. 7184-7201
  • DOI: 10.1002/anie.200604504

Recent Advances in Hydrotreating of Pyrolysis Bio-Oil and Its Oxygen-Containing Model Compounds
journal, April 2013

  • Wang, Huamin; Male, Jonathan; Wang, Yong
  • ACS Catalysis, Vol. 3, Issue 5
  • DOI: 10.1021/cs400069z

Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering
journal, September 2006

  • Huber, George W.; Iborra, Sara; Corma, Avelino
  • Chemical Reviews, Vol. 106, Issue 9, p. 4044-4098
  • DOI: 10.1021/cr068360d

A roadmap for conversion of lignocellulosic biomass to chemicals and fuels
journal, August 2012

  • Wettstein, Stephanie G.; Alonso, David Martin; Gürbüz, Elif I.
  • Current Opinion in Chemical Engineering, Vol. 1, Issue 3
  • DOI: 10.1016/j.coche.2012.04.002

Furfural-A Promising Platform for Lignocellulosic Biofuels
journal, December 2011

  • Lange, Jean-Paul; van der Heide, Evert; van Buijtenen, Jeroen
  • ChemSusChem, Vol. 5, Issue 1
  • DOI: 10.1002/cssc.201100648

Production of 2-Methylfuran by Vapor-Phase Hydrogenation of Furfural
journal, March 1948

  • Burnett, L. W.; Johns, I. B.; Holdren, R. F.
  • Industrial & Engineering Chemistry, Vol. 40, Issue 3
  • DOI: 10.1021/ie50459a034

Selective conversion of furfural to methylfuran over silica-supported NiFe bimetallic catalysts
journal, November 2011


Understanding the Role of M/Pt(111) (M = Fe, Co, Ni, Cu) Bimetallic Surfaces for Selective Hydrodeoxygenation of Furfural
journal, August 2017


Monolayer bimetallic surfaces: Experimental and theoretical studies of trends in electronic and chemical properties
journal, May 2008


Platinum-Like Behavior of Tungsten Carbide in Surface Catalysis
journal, August 1973


Atom beam sputtered Mo2C films as a diffusion barrier for copper metallization
journal, January 2009


Selective Hydrodeoxygenation of Biomass-Derived Oxygenates to Unsaturated Hydrocarbons using Molybdenum Carbide Catalysts
journal, April 2013


Molybdenum Carbide as a Highly Selective Deoxygenation Catalyst for Converting Furfural to 2-Methylfuran
journal, April 2014


Water-Gas-Shift Reaction on Molybdenum Carbide Surfaces:  Essential Role of the Oxycarbide
journal, October 2006

  • Liu, Ping; Rodriguez, José A.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 39
  • DOI: 10.1021/jp0621629

Ab initiomolecular dynamics for liquid metals
journal, January 1993


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation
journal, September 1992


Trends in the chemical properties of early transition metal carbide surfaces: A density functional study
journal, July 2005


Differentiation of O–H and C–H Bond Scission Mechanisms of Ethylene Glycol on Pt and Ni/Pt Using Theory and Isotopic Labeling Experiments
journal, May 2011

  • Salciccioli, Michael; Yu, Weiting; Barteau, Mark A.
  • Journal of the American Chemical Society, Vol. 133, Issue 20
  • DOI: 10.1021/ja201801t

Effects of bimetallic modification on the decomposition of CH3OH and H2O on Pt/W(110) bimetallic surfaces
journal, October 2010


Reactions of methanol and water over carbide-modified Mo()
journal, June 2003


Reaction of Ethylene with Clean and Carbide-Modified Mo(110):  Converting Surface Reactivities of Molybdenum to Pt-Group Metals
journal, January 1996

  • Frühberger, B.; Chen, J. G.
  • Journal of the American Chemical Society, Vol. 118, Issue 46
  • DOI: 10.1021/ja960656l

Reactivities of carbon‐ and nitrogen‐modified Mo(110): A comparison of modification effects by surface and interstitial adatoms
journal, May 1996

  • Frühberger, B.; Chen, J. G.; Eng, J.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 14, Issue 3
  • DOI: 10.1116/1.579972

Reaction Pathways of Propanal and 1-Propanol on Fe/Ni(111) and Cu/Ni(111) Bimetallic Surfaces
journal, May 2014

  • Myint, MyatNoeZin; Yan, Yushan; Chen, Jingguang G.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 21
  • DOI: 10.1021/jp501208q

Vibrational properties of levulinic acid and furan derivatives: Raman spectroscopy and theoretical calculations
journal, May 2011

  • Kim, Taejin; Assary, Rajeev S.; Curtiss, Larry A.
  • Journal of Raman Spectroscopy, Vol. 42, Issue 12
  • DOI: 10.1002/jrs.2951

Mechanisms of Mo 2 C(101)-Catalyzed Furfural Selective Hydrodeoxygenation to 2-Methylfuran from Computation
journal, September 2016


Works referencing / citing this record:

Vibrational Spectroscopic Characterization of Glycerol Reaction Pathways over Metal‐Modified Molybdenum Carbide Surfaces
journal, October 2019


Catalyst-free synthesis of biodiesel precursors from biomass-based furfuryl alcohols in the presence of H 2 O and air
journal, January 2019

  • Qin, Shengxiang; Li, Teng; Zhang, Man
  • Green Chemistry, Vol. 21, Issue 23
  • DOI: 10.1039/c9gc03179k