Insights into the Ring‐Opening of Biomass‐Derived Furanics over Carbon‐Supported Ruthenium
Abstract
Abstract The 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 a combined experimental and computational investigation to provide insights into the 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. DFT calculations and microkinetic modeling indicate that DMF adsorbs on Ru in an open‐ring configuration, which is potentially a common surface intermediate that leads to both ring‐opening and ring‐saturation products. Although the activation barriers for the two pathways are comparable, the 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 to determine the product distribution: the former favors less bulky, that is, ring‐closed, intermediates, and the latter retards O−H bond formation. Finally, we show that the hydrodeoxygenation of oxygenated furanics, such as 5‐methylfurfural and (5‐methyl‐2‐furyl)methanol, on Ru occurs preferentially at oxygen‐containing side groups to form DMF, followed by either ring‐opening or ring‐saturation.
- Authors:
-
[1]
- Catalysis Center for Energy Innovation Department of Chemical and Biomolecular Engineering University of Delaware Newark Delaware 19716 United States
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1400585
- Grant/Contract Number:
- SC0001004
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- ChemSusChem
- Additional Journal Information:
- Journal Name: ChemSusChem Journal Volume: 9 Journal Issue: 21; Journal ID: ISSN 1864-5631
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Gilkey, Matthew J., Mironenko, Alexander V., Yang, Leerang, Vlachos, Dionisios G., and Xu, Bingjun. Insights into the Ring‐Opening of Biomass‐Derived Furanics over Carbon‐Supported Ruthenium. Germany: N. p., 2016.
Web. doi:10.1002/cssc.201600681.
Gilkey, Matthew J., Mironenko, Alexander V., Yang, Leerang, Vlachos, Dionisios G., & Xu, Bingjun. Insights into the Ring‐Opening of Biomass‐Derived Furanics over Carbon‐Supported Ruthenium. Germany. https://doi.org/10.1002/cssc.201600681
Gilkey, Matthew J., Mironenko, Alexander V., Yang, Leerang, Vlachos, Dionisios G., and Xu, Bingjun. Fri .
"Insights into the Ring‐Opening of Biomass‐Derived Furanics over Carbon‐Supported Ruthenium". Germany. https://doi.org/10.1002/cssc.201600681.
@article{osti_1400585,
title = {Insights into the Ring‐Opening of Biomass‐Derived Furanics over Carbon‐Supported Ruthenium},
author = {Gilkey, Matthew J. and Mironenko, Alexander V. and Yang, Leerang and Vlachos, Dionisios G. and Xu, Bingjun},
abstractNote = {Abstract The 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 a combined experimental and computational investigation to provide insights into the 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. DFT calculations and microkinetic modeling indicate that DMF adsorbs on Ru in an open‐ring configuration, which is potentially a common surface intermediate that leads to both ring‐opening and ring‐saturation products. Although the activation barriers for the two pathways are comparable, the 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 to determine the product distribution: the former favors less bulky, that is, ring‐closed, intermediates, and the latter retards O−H bond formation. Finally, we show that the hydrodeoxygenation of oxygenated furanics, such as 5‐methylfurfural and (5‐methyl‐2‐furyl)methanol, on Ru occurs preferentially at oxygen‐containing side groups to form DMF, followed by either ring‐opening or ring‐saturation.},
doi = {10.1002/cssc.201600681},
journal = {ChemSusChem},
number = 21,
volume = 9,
place = {Germany},
year = {Fri Oct 14 00:00:00 EDT 2016},
month = {Fri Oct 14 00:00:00 EDT 2016}
}
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