Poisoning of Ru/C by homogeneous Brønsted acids in hydrodeoxygenation of 2,5-dimethylfuran via catalytic transfer hydrogenation
Abstract
It has been proposed that the combination of metal and acid sites is critical for effective ring opening of biomass-derived furans to linear molecules, a reaction that holds promise for the production of renewable polymer precursors and alkanes. As such, in this work, we use 2,5-dimethylfuran (DMF) as a model compound to investigate hydrogenolysis and hydrogenation pathways using a combination of H2SO4 and Ru-mediated catalytic transfer hydrogenation in 2-propanol. Acid-catalyzed hydrolytic ring opening of DMF to 2,5-hexanedione (HDN) occurs readily at 80 °C with a selectivity of 89% in 2-propanol. Over Ru/C, HDN is fully converted after only 2 h at 80 °C, forming a mixture of both ring-closed products (~68% total yield), i.e., 2,5-dimethyltetrahydrofuran (DMTHF) and 2,5-dimethyl-2,3-dihydrofuran (DMDHF), as well as ring opened products (~28% total yield), i.e., 2,5-hexanediol (2,5-HDL) and 2-hexanol (HOL). Rather than observing sequential hydrolysis/hydrogenation reactions, we observe severe suppression of metal chemistry when having both Ru/C and H2SO4 in the reaction system. While minor leaching of Ru occurs in the presence of mineral acids, X-ray photoelectron spectroscopy coupled with CO chemisorption studies suggest that the primary cause of the lack of Ru-mediated chemistry is poisoning by strongly adsorbed sulfate species. This hypothesis is supported bymore »
- Authors:
-
- Univ. of Delaware, Newark, DE (United States). Catalysis Center for Energy Innovation (CCEI) and Dept. of Chemical and Biomolecular Engineering
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1469845
- Grant/Contract Number:
- SC0001004
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Applied Catalysis. A, General
- Additional Journal Information:
- Journal Volume: 542; Journal Issue: C; 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; Journal ID: ISSN 0926-860X
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 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)
Citation Formats
Gilkey, Matthew J., Vlachos, Dionisios G., and Xu, Bingjun. Poisoning of Ru/C by homogeneous Brønsted acids in hydrodeoxygenation of 2,5-dimethylfuran via catalytic transfer hydrogenation. United States: N. p., 2017.
Web. doi:10.1016/j.apcata.2017.06.010.
Gilkey, Matthew J., Vlachos, Dionisios G., & Xu, Bingjun. Poisoning of Ru/C by homogeneous Brønsted acids in hydrodeoxygenation of 2,5-dimethylfuran via catalytic transfer hydrogenation. United States. https://doi.org/10.1016/j.apcata.2017.06.010
Gilkey, Matthew J., Vlachos, Dionisios G., and Xu, Bingjun. Tue .
"Poisoning of Ru/C by homogeneous Brønsted acids in hydrodeoxygenation of 2,5-dimethylfuran via catalytic transfer hydrogenation". United States. https://doi.org/10.1016/j.apcata.2017.06.010. https://www.osti.gov/servlets/purl/1469845.
@article{osti_1469845,
title = {Poisoning of Ru/C by homogeneous Brønsted acids in hydrodeoxygenation of 2,5-dimethylfuran via catalytic transfer hydrogenation},
author = {Gilkey, Matthew J. and Vlachos, Dionisios G. and Xu, Bingjun},
abstractNote = {It has been proposed that the combination of metal and acid sites is critical for effective ring opening of biomass-derived furans to linear molecules, a reaction that holds promise for the production of renewable polymer precursors and alkanes. As such, in this work, we use 2,5-dimethylfuran (DMF) as a model compound to investigate hydrogenolysis and hydrogenation pathways using a combination of H2SO4 and Ru-mediated catalytic transfer hydrogenation in 2-propanol. Acid-catalyzed hydrolytic ring opening of DMF to 2,5-hexanedione (HDN) occurs readily at 80 °C with a selectivity of 89% in 2-propanol. Over Ru/C, HDN is fully converted after only 2 h at 80 °C, forming a mixture of both ring-closed products (~68% total yield), i.e., 2,5-dimethyltetrahydrofuran (DMTHF) and 2,5-dimethyl-2,3-dihydrofuran (DMDHF), as well as ring opened products (~28% total yield), i.e., 2,5-hexanediol (2,5-HDL) and 2-hexanol (HOL). Rather than observing sequential hydrolysis/hydrogenation reactions, we observe severe suppression of metal chemistry when having both Ru/C and H2SO4 in the reaction system. While minor leaching of Ru occurs in the presence of mineral acids, X-ray photoelectron spectroscopy coupled with CO chemisorption studies suggest that the primary cause of the lack of Ru-mediated chemistry is poisoning by strongly adsorbed sulfate species. This hypothesis is supported by the observation of Ru-catalyzed chemistry when replacing H2SO4 with Nafion, a solid Brønsted acid, as sulfonic acid groups tethered to the polymer backbone cannot adsorb on the metal sites.},
doi = {10.1016/j.apcata.2017.06.010},
journal = {Applied Catalysis. A, General},
number = C,
volume = 542,
place = {United States},
year = {Tue Jun 06 00:00:00 EDT 2017},
month = {Tue Jun 06 00:00:00 EDT 2017}
}
Web of Science