Insights into ring opening of biomass-derived furanics over Ru/C
Date
2016-10-14
Journal Title
Journal ISSN
Volume Title
Publisher
Wiley Online
Abstract
Selective ring opening of cellulose-derived furanic molecules is a promising pathway for the production of industrially relevant linear oxygenates, such as 1,6-hexanediol. 2,5-dimethylfuran (DMF) is employed as a model compound in combined experimental and computational investigations to provide insights into metal-catalyzed ring opening. Ring opening to 2-hexanol and 2-hexanone and ring saturation to 2,5-dimethyltetrahydrofuran (DMTHF) are identified as two main parallel pathways. Density functional theory calculations and microkinetic modeling indicate DMF adsorbs on Ru in an open-ring configuration, which is potentially a common surface intermediate leading to both ring opening and ring saturation products. While the activation barriers for the two pathways are comparable, formation of DMTHF is more thermodynamically favorable. In addition, steric interactions with co-adsorbed 2-propoxyl, derived from the solvent, and the oxophilic nature of Ru play key roles in determining the product distribution: the former favors less bulky, i.e., ring-closed, intermediates, and the latter retards O-H bond formation. Finally, we show that hydrodeoxygenation of oxygenated furanics, such as 5-methylfurfural and (5-methyl-2-furyl)methanol, on Ru preferentially occurs at oxygen-containing side groups to form DMF, followed by either ring opening or ring saturation.
Description
Author's final draft after peer review
Keywords
Citation
Gilkey, Matthew J., et al. "Insights into the Ring‐Opening of Biomass‐Derived Furanics over Carbon‐Supported Ruthenium." ChemSusChem 9.21 (2016): 3113-3121.