Mechanistic Insights into Metal Lewis Acid-Mediated Catalytic Transfer Hydrogenation of Furfural to 2-Methylfuran

Gilkey, Matthew J.; Panagiotopoulou, Paraskevi; Mironenko, Alexander V.; Jenness, Glen R.; Vlachos, Dionisios G.; Xu, Bingjun

doi:10.1021/acscatal.5b00586

Title: Mechanistic Insights into Metal Lewis Acid-Mediated Catalytic Transfer Hydrogenation of Furfural to 2-Methylfuran

Journal Article · Tue May 19 00:00:00 EDT 2015 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.5b00586· OSTI ID:1246456

Gilkey, Matthew J. ^[1]; Panagiotopoulou, Paraskevi ^[1]; Mironenko, Alexander V. ^[1]; Jenness, Glen R. ^[1]; Vlachos, Dionisios G. ^[1]; Xu, Bingjun ^[1]

Catalysis Center for Energy Innovation, Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, Delaware 19716, United States

Biomass conversion to fuels and chemicals provides sustainability, but the highly oxygenated nature of a large fraction of biomass-derived molecules requires removal of the excess oxygen and partial hydrogenation in the upgrade, typically met by hydrodeoxygenation processes. Catalytic transfer hydrogenation is a general approach in accomplishing this with renewable organic hydrogen donors, but mechanistic understanding is currently lacking. Here, we elucidate the molecular level reaction pathway of converting hemicellulose-derived furfural to 2-methylfuran on a bifunctional Ru/RuO_x/C catalyst using isopropyl alcohol as the hydrogen donor via a combination of isotopic labeling and kinetic studies. Hydrogenation of the carbonyl group of furfural to furfuryl alcohol proceeds through a Lewis acid-mediated intermolecular hydride transfer and hydrogenolysis of furfuryl alcohol occurs mainly via ring-activation involving both metal and Lewis acid sites. Our results show that the bifunctional nature of the catalyst is critical in the efficient hydrodeoxygenation of furanics and provides insights toward the rational design of such catalysts.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI); Univ. of Delaware, Newark, DE (United States)

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

Grant/Contract Number:: SC0001004

OSTI ID:: 1246456

Alternate ID(s):: OSTI ID: 1385961

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Vol. 5 Journal Issue: 7; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 196 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalytic transfer hydrogenation
bifunctional
mechanism
ring activation
furfural
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catalysis (heterogeneous)
biofuels (including algae and biomass)
bio-inspired
hydrogen and fuel cells
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Title: Mechanistic Insights into Metal Lewis Acid-Mediated Catalytic Transfer Hydrogenation of Furfural to 2-Methylfuran

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