DFT Study of the Conversion of Furfuryl Alcohol to 2-Methylfuran on RuO2 (110)

Jenness, Glen R.; Vlachos, Dionisios G.

doi:10.1021/jp5109015

Title: DFT Study of the Conversion of Furfuryl Alcohol to 2-Methylfuran on RuO₂ (110)

Journal Article · Wed Feb 18 00:00:00 EST 2015 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/jp5109015· OSTI ID:1385386

Jenness, Glen R. ^[1]; Vlachos, Dionisios G. ^[1]

Univ. of Delaware, Newark, DE (United States)

Recently, our group proposed the catalytic transfer hydrogenation for refining biomass-derived 5-hydroxymethylfurfural and furfural to 2,5-dimethylfuran and 2-methylfuran, respectively. With a metallic Ru/C catalyst, a selectivity of ~30% was achieved. The promotion of the Ru/C catalyst with the Lewis acid RuO_x resulted in a selectivity of ~80%. In the current study, we employ density functional theory calculations on the RuO₂ (110) surface in order to elucidate the role of the Lewis acidity in the reduction of the biomass-derived furfuryl alcohol to 2-methylfuran. We identify the rate-limiting step to be the scission of the C–O bond of the side chain. In addition, we find evidence for the activation of the furan ring via an insertion of a hydrogen atom. However, the Lewis basicity of a neighboring bridging oxygen results in the furan ring being deactivated. Finally, the formation of water from the reduction process is facile. However, owing to the strong binding energy between the RuO₂ surface and the water molecule, poisoning of the catalytic surface by adsorbed water is possible. Lastly, we show that the RuO₂ (110) carries out the reduction of furfural to furfuryl alcohol via the Meerwin–Ponndorf–Verley (MPV) reaction fairly easily, consistent with published experimental data.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI)

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

Grant/Contract Number:: SC0001004; AC02-05CH11231

OSTI ID:: 1385386

Journal Information:: Journal of Physical Chemistry. C, Vol. 119, Issue 11; Related Information: CCEI partners with the University of Delaware (lead); Brookhaven National Laboratory; California Institute of Technology; Columbia University; University of Delaware; Lehigh University; University of Massachusetts, Amherst; Massachusetts Institute of Technology; University of Minnesota; Pacific Northwest National Laboratory; University of Pennsylvania; Princeton University; Rutgers University; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 31 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalysis (homogeneous)
catalysis (heterogeneous)
biofuels (including algae and biomass)
bio-inspired
hydrogen and fuel cells
materials and chemistry by design
synthesis (novel materials)
synthesis (self-assembly)
synthesis (scalable processing)
hydrogen
chemical reactions
alcohols
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Title: DFT Study of the Conversion of Furfuryl Alcohol to 2-Methylfuran on RuO2 (110)

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Title: DFT Study of the Conversion of Furfuryl Alcohol to 2-Methylfuran on RuO₂ (110)