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Investigating Reaction Mechanisms for Furfural Hydrodeoxygenation on Ni and the Effect of Boron Doping on the Activity and Selectivity of the Catalyst

  • Arghya Banerjee
    Arghya Banerjee
    School of Chemical and Biomedical Engineering, Nanyang Technological University, 62 Nanyang Drive, Singapore 637459
    Central Institute of Mining and Fuel Research (CIMFR), Digwadih Campus, PO FRI, 828108 Dhanbad, Jharkhand, India
  •  and 
  • Samir H. Mushrif*
    Samir H. Mushrif
    School of Chemical and Biomedical Engineering, Nanyang Technological University, 62 Nanyang Drive, Singapore 637459
    Department of Chemical and Materials Engineering, University of Alberta, 9211-116 St NW, Edmonton, Alberta T6G 1H9, Canada
    *E-mail: [email protected] (S.H.M.).
Cite this: J. Phys. Chem. C 2018, 122, 32, 18383–18394
Publication Date (Web):July 23, 2018
https://doi.org/10.1021/acs.jpcc.8b01301
Copyright © 2018 American Chemical Society

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    Abstract

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    Fast pyrolysis is a promising route for the production of fuels and high value chemicals from non-fossil fuel resources like biomass. However, the design of active and inexpensive catalysts that can selectively convert furfural, an important component in pyrolysis derived bio-oil, to target chemicals remains a challenge. In this context, Ni-based catalysts are potential candidates for the vapor phase activation of furfural in the presence of H2. In this paper, mechanisms and energetics (kinetics and thermodynamics) of the catalytic conversion of furfural to furans, furfuryl alcohol, and C4 products in the presence of H2 on Ni(111) are established, and the experimentally observed change in the selectivity with temperature is explained, using first-principles density functional theory. Hydrogen adsorbs stronger than furfural on the Ni surface. At low operating temperatures, hydrogen adsorption is spontaneous, leading to high hydrogen surface coverages that favor furfural hydrogenation and decarbonylation over ring-opening, to form furfuryl alcohol and furans. At higher temperatures, hydrogen adsorption is not thermodynamically favorable, leading to a relatively clean Ni surface on which furfural ring-opening and decarbonylation are favored, leading to C4 products and furans. We reveal that the incorporation of subsurface boron in Ni leads to a corrugated catalyst surface (NiB) on which furfural adsorbs stronger than hydrogen. The free energy barriers for the formation of furans and C4 products are also considerably lower in the presence of boron, suggesting an enhanced catalytic activity of NiB. Thus, we propose that the boron-doped Ni catalyst is a potential candidate for selectively converting furfural to furan and C4 products at lower operating temperatures, relative to Ni.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.8b01301.

    • S1.1: effect of H coverage on the H adsorption energies on Ni(111) surfaces; SI.2: calculation of free energy of adsorption of furfural on Ni(111); SI.3: convergence studies: effect of slab thickness, vacuum layer spacing, and unit cell size on furfural binding energy; SI.4: reaction rates for the first step of furfural activation on Ni surfaces; SI.5: detailed energetics of furfural activation on clean Ni(111), H-saturated Ni(111), and subsurface boron-doped Ni (NiB) surfaces (PDF)

    • Vibrational frequencies of the TS and intermediates computed in this study (XLSX)

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