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Title: Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates

In this paper, the rates of Brønsted-acid-catalyzed reactions of ethyl tert-butyl ether, tert-butanol, levoglucosan, 1,2-propanediol, fructose, cellobiose, and xylitol were measured in solvent mixtures of water with three polar aprotic cosolvents: γ-valerolactone; 1,4-dioxane; and tetrahydrofuran. As the water content of the solvent environment decreases, reactants with more hydroxyl groups have higher catalytic turnover rates for both hydrolysis and dehydration reactions. We present classical molecular dynamics simulations to explain these solvent effects in terms of three simulation-derived observables: (1) the extent of water enrichment in the local solvent domain of the reactant; (2) the average hydrogen bonding lifetime between water molecules and the reactant; and (3) the fraction of the reactant accessible surface area occupied by hydroxyl groups, all as a function of solvent composition. Finally, we develop a model, constituted by linear combinations of these three observables, that predicts experimentally determined rate constants as a function of solvent composition for the entire set of acid-catalyzed reactions.
Authors:
ORCiD logo [1] ; ORCiD logo [1] ;  [2] ; ORCiD logo [3] ; ORCiD logo [4] ; ORCiD logo [1] ; ORCiD logo [1] ;  [3]
  1. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering
  2. Chinese Academy of Sciences (CAS), Dalian (China). Dalian National Lab. for Clean Energy. Dalian Inst. of Chemical Physics; Univ. of Chinese Academy of Sciences, Beijing (China)
  3. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering. DOE Great Lakes Bioenergy Research Center
  4. Chinese Academy of Sciences (CAS), Dalian (China). Dalian National Lab. for Clean Energy. Dalian Inst. of Chemical Physics
Publication Date:
Grant/Contract Number:
EE0006878; FC02-07ER64494; ACI-1548562
Type:
Accepted Manuscript
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Volume: 11; Journal Issue: 3; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry
Research Org:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (EE-3B); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); Wisconsin Alumni Research Foundation (United States); National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1475402

Walker, Theodore W., Chew, Alex K., Li, Huixiang, Demir, Benginur, Zhang, Z. Conrad, Huber, George W., Van Lehn, Reid C., and Dumesic, James A.. Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates. United States: N. p., Web. doi:10.1039/C7EE03432F.
Walker, Theodore W., Chew, Alex K., Li, Huixiang, Demir, Benginur, Zhang, Z. Conrad, Huber, George W., Van Lehn, Reid C., & Dumesic, James A.. Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates. United States. doi:10.1039/C7EE03432F.
Walker, Theodore W., Chew, Alex K., Li, Huixiang, Demir, Benginur, Zhang, Z. Conrad, Huber, George W., Van Lehn, Reid C., and Dumesic, James A.. 2018. "Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates". United States. doi:10.1039/C7EE03432F.
@article{osti_1475402,
title = {Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates},
author = {Walker, Theodore W. and Chew, Alex K. and Li, Huixiang and Demir, Benginur and Zhang, Z. Conrad and Huber, George W. and Van Lehn, Reid C. and Dumesic, James A.},
abstractNote = {In this paper, the rates of Brønsted-acid-catalyzed reactions of ethyl tert-butyl ether, tert-butanol, levoglucosan, 1,2-propanediol, fructose, cellobiose, and xylitol were measured in solvent mixtures of water with three polar aprotic cosolvents: γ-valerolactone; 1,4-dioxane; and tetrahydrofuran. As the water content of the solvent environment decreases, reactants with more hydroxyl groups have higher catalytic turnover rates for both hydrolysis and dehydration reactions. We present classical molecular dynamics simulations to explain these solvent effects in terms of three simulation-derived observables: (1) the extent of water enrichment in the local solvent domain of the reactant; (2) the average hydrogen bonding lifetime between water molecules and the reactant; and (3) the fraction of the reactant accessible surface area occupied by hydroxyl groups, all as a function of solvent composition. Finally, we develop a model, constituted by linear combinations of these three observables, that predicts experimentally determined rate constants as a function of solvent composition for the entire set of acid-catalyzed reactions.},
doi = {10.1039/C7EE03432F},
journal = {Energy & Environmental Science},
number = 3,
volume = 11,
place = {United States},
year = {2018},
month = {2}
}

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