Poisoning of Ru/C by Homogeneous Brønsted Acids in Hydrodeoxygenation of 2,5-Dimethylfuran via Catalytic Transfer Hydrogenation
| Author(s) | Gilkey, Matthew J. | |
| Author(s) | Vlachos, Dionisios G. | |
| Author(s) | Xu, Bingjun | |
| Ordered Author | Matthew J. Gilkey, Dionisios G. Vlachos, Bingjun Xu | |
| UD Author | Gilkey, Matthew J. | en_US |
| UD Author | Vlachos, Dionisios G | en_US |
| UD Author | Xu, Bingjun | en_US |
| Date Accessioned | 2018-05-30T14:55:18Z | |
| Date Available | 2018-05-30T14:55:18Z | |
| Copyright Date | Copyright © 2017 American Chemical Society | en_US |
| Publication Date | 2017 | |
| Description | Author's final draft after peer review | en_US |
| 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. 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. | en_US |
| Department | University of Delaware. Department of Chemical & Biomolecular Engineering. | en_US |
| Citation | Gilkey, Matthew J., Dionisios G. Vlachos, and Bingjun Xu. "Poisoning of Ru/C by homogeneous Brønsted acids in hydrodeoxygenation of 2, 5-dimethylfuran via catalytic transfer hydrogenation." Applied Catalysis A: General 542 (2017): 327-335. | en_US |
| DOI | https://doi.org/10.1016/j.apcata.2017.06.010 | en_US |
| ISSN | 0926-860X | en_US |
| URL | http://udspace.udel.edu/handle/19716/23542 | |
| Language | en_US | en_US |
| Publisher | Elsevier | en_US |
| dc.rights | Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. | en_US |
| dc.rights | Manuscript is made available in accordance with the University of Delaware Faculty Policy on Open Access and the publisher's policy | en_US |
| dc.source | Applied Catalysis A: General | en_US |
| dc.source.uri | https://www.sciencedirect.com/journal/applied-catalysis-a-general | en_US |
| Title | Poisoning of Ru/C by Homogeneous Brønsted Acids in Hydrodeoxygenation of 2,5-Dimethylfuran via Catalytic Transfer Hydrogenation | en_US |
| Type | Article | en_US |