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Title: Investigation of solvent effects in the hydrodeoxygenation of levulinic acid to γ-valerolactone over Ru catalysts

Abstract

Liquid phase, reductive deoxygenation of biomass derived platform chemicals over transition metal surfaces constitutes an efficient scheme for upgrading lignocellulosic biomass. The solvation effects on the reaction kinetics of the hydrodeoxygenation (HDO) of levulinic acid (LA) towards the formation of γ-valerolactone (GVL) over Ru(0 0 0 1) has been studied in three condensed phase media, i.e., liquid water, methanol, and 1,4-dioxane. Detailed microkinetic models have been developed incorporating various catalytic pathways including formation of 4-hydroxypentanoic acid (HPA) and α-angelicalactone (AGL) to simulate the catalytic activity of Ru(0 0 0 1) under various reaction conditions of solvent, temperature, and partial pressures. Our microkinetic models suggest that direct catalytic conversion with alkoxy formation is the preferred reaction mechanism in all reaction environments. Furthermore, we find that water facilitates the reaction kinetics significantly and that the solvent effect is strongest at lower temperatures (T < 373 K). In this work, rate increases due to liquid water solvation effects of 2–4 orders of magnitude are observed. All solvents increase the rate of reaction relative to the gas phase; however, solvation effects decrease with decrease in polarity. 1,4-dioxane increases the rate only minimally due to competitive adsorption of the solvent molecules despite facilitating the partiallymore » rate controlling step of the LA hydrogenation to an alkoxy intermediate.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of South Carolina, Columbia, SC (United States)
  2. Syracuse Univ., NY (United States)
Publication Date:
Research Org.:
Univ. of South Carolina, Columbia, SC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1656903
Alternate Identifier(s):
OSTI ID: 1570060
Grant/Contract Number:  
SC0007167; CBET-1159863; CBET-1159739; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Catalysis
Additional Journal Information:
Journal Volume: 379; Journal ID: ISSN 0021-9517
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; solvent effects; ruthenium; density functional theory (DFT); hydrodeoxygenation; biomass; microkinetic modeling; levulinic acid; water; 1,4-Dioxane; y-Valerolactone

Citation Formats

Mamun, Osman, Saleheen, Mohammad, Bond, Jesse Q., and Heyden, Andreas. Investigation of solvent effects in the hydrodeoxygenation of levulinic acid to γ-valerolactone over Ru catalysts. United States: N. p., 2019. Web. https://doi.org/10.1016/j.jcat.2019.09.026.
Mamun, Osman, Saleheen, Mohammad, Bond, Jesse Q., & Heyden, Andreas. Investigation of solvent effects in the hydrodeoxygenation of levulinic acid to γ-valerolactone over Ru catalysts. United States. https://doi.org/10.1016/j.jcat.2019.09.026
Mamun, Osman, Saleheen, Mohammad, Bond, Jesse Q., and Heyden, Andreas. Fri . "Investigation of solvent effects in the hydrodeoxygenation of levulinic acid to γ-valerolactone over Ru catalysts". United States. https://doi.org/10.1016/j.jcat.2019.09.026. https://www.osti.gov/servlets/purl/1656903.
@article{osti_1656903,
title = {Investigation of solvent effects in the hydrodeoxygenation of levulinic acid to γ-valerolactone over Ru catalysts},
author = {Mamun, Osman and Saleheen, Mohammad and Bond, Jesse Q. and Heyden, Andreas},
abstractNote = {Liquid phase, reductive deoxygenation of biomass derived platform chemicals over transition metal surfaces constitutes an efficient scheme for upgrading lignocellulosic biomass. The solvation effects on the reaction kinetics of the hydrodeoxygenation (HDO) of levulinic acid (LA) towards the formation of γ-valerolactone (GVL) over Ru(0 0 0 1) has been studied in three condensed phase media, i.e., liquid water, methanol, and 1,4-dioxane. Detailed microkinetic models have been developed incorporating various catalytic pathways including formation of 4-hydroxypentanoic acid (HPA) and α-angelicalactone (AGL) to simulate the catalytic activity of Ru(0 0 0 1) under various reaction conditions of solvent, temperature, and partial pressures. Our microkinetic models suggest that direct catalytic conversion with alkoxy formation is the preferred reaction mechanism in all reaction environments. Furthermore, we find that water facilitates the reaction kinetics significantly and that the solvent effect is strongest at lower temperatures (T < 373 K). In this work, rate increases due to liquid water solvation effects of 2–4 orders of magnitude are observed. All solvents increase the rate of reaction relative to the gas phase; however, solvation effects decrease with decrease in polarity. 1,4-dioxane increases the rate only minimally due to competitive adsorption of the solvent molecules despite facilitating the partially rate controlling step of the LA hydrogenation to an alkoxy intermediate.},
doi = {10.1016/j.jcat.2019.09.026},
journal = {Journal of Catalysis},
number = ,
volume = 379,
place = {United States},
year = {2019},
month = {10}
}

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Cited by: 8 works
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