Issue 3, 2018

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

Abstract

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. 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.

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

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
02 दिसम्बर 2017
Accepted
08 फरवरी 2018
First published
08 फरवरी 2018

Energy Environ. Sci., 2018,11, 617-628

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

T. W. Walker, A. K. Chew, H. Li, B. Demir, Z. C. Zhang, G. W. Huber, R. C. Van Lehn and J. A. Dumesic, Energy Environ. Sci., 2018, 11, 617 DOI: 10.1039/C7EE03432F

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements