TY - JOUR
T1 - Insights into the Ring-Opening of Biomass-Derived Furanics over Carbon-Supported Ruthenium
AU - Gilkey, Matthew J.
AU - Mironenko, Alexander V.
AU - Yang, Leerang
AU - Vlachos, Dionisios G.
AU - Xu, Bingjun
N1 - Funding Information:
We acknowledge support from the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award number DE-SC0001004.
Publisher Copyright:
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2016/11/9
Y1 - 2016/11/9
N2 - 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.
AB - 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.
KW - biomass
KW - hydrogenation
KW - reaction mechanisms
KW - ruthenium
KW - supported catalysts
UR - http://www.scopus.com/inward/record.url?scp=84994462646&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84994462646&partnerID=8YFLogxK
U2 - 10.1002/cssc.201600681
DO - 10.1002/cssc.201600681
M3 - Article
C2 - 27739655
AN - SCOPUS:84994462646
VL - 9
SP - 3113
EP - 3121
JO - ChemSusChem
JF - ChemSusChem
SN - 1864-5631
IS - 21
ER -