@article{34b62925bb8c44f6b128d2ef60802f32,
title = "Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates",
abstract = "The rates of Br{\o}nsted-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. 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.",
author = "Walker, {Theodore W.} and Chew, {Alex K.} and Huixiang Li and Benginur Demir and Zhang, {Z. Conrad} and Huber, {George W.} and {Van Lehn}, {Reid C.} and Dumesic, {James A.}",
note = "Funding Information: This work was supported in part by: the Department of Energy, Office of Energy Efficiency and Renewable Energy (EERE), under Award Number DE-EE0006878; by the U.S. Department of Energy, Office of Basic Energy Sciences; and by the DOE Great Lakes Bioenergy Research Center (http://www.glbrc.org). The U.S. Department of Energy, Office of Sciences, Office of Biological and Environmental Research support the GLBRC, through the cooperative agreement BER DE-FC02-07ER64494 between the Board of Regents of the University of Wisconsin and the U.S. Department of Energy. T. W. Walker acknowledges that this material is based on work supported by the Office of the Vice Chancellor for Research and Graduate Education at the University of Wisconsin-Madison with funding from the Wisconsin Alumni Research Foundation. This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant number ACI-1548562. This work also used the computing resources and assistance of the UW-Madison Center for High Throughput Computing (CHTC) in the Department of Computer Sciences. The CHTC is supported by UW-Madison, the Advanced Computing Initiative, the Wisconsin Alumni Research Foundation, the Wisconsin Institutes for Discovery, and the National Science Foundation, and is an active member of the Open Science Grid, which is supported by the National Science Foundation and the U.S. Department of Energy{\textquoteright}s Office of Science. We acknowledge Liam Witteman for help in carrying out the reaction kinetics studies. We thank Dr. Max A. Mellmer for thoughtful discussions regarding organic solvent effects in acid-catalyzed reactions. Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2018.",
year = "2018",
month = mar,
doi = "10.1039/c7ee03432f",
language = "English (US)",
volume = "11",
pages = "617--628",
journal = "Energy and Environmental Science",
issn = "1754-5692",
publisher = "Royal Society of Chemistry",
number = "3",
}