These reactions are typically performed in aqueous solution where extensive control over reaction kinetics and selectivity is available by tuning the temperature, catalyst, and solvent composition ( Huber et al., 2006 Chheda et al., 2007 Román-Leshkov et al., 2007 Mellmer et al., 2014b Motagamwala et al., 2016 He et al., 2017 Won et al., 2017 Sener et al., 2018). For example, cellulose, one of the primary components of lignocellulosic biomass, can be converted through a series of dehydration and hydrolysis reactions to form 5-hydroxymethylfurfural, a platform chemical for fuels and other commodity chemicals ( Chheda et al., 2007 Corma et al., 2007 Román-Leshkov et al., 2007 Pagan-Torres et al., 2012 Mellmer et al., 2015 He et al., 2017). The catalytic upgrading of biomass (e.g., wood, crops, etc.) is a promising strategy to obtain valuable chemicals from renewable resources while limiting waste products ( Huber et al., 2006 Stöcker, 2008 Tock et al., 2010 Shuai and Luterbacher, 2016 Nguyen et al., 2017 Walker et al., 2019). These results demonstrate the ability of classical molecular dynamics simulations to screen solvent systems for improved acid-catalyzed reaction performance. The revised model is able to predict experimental reaction rates across solvent systems with different organic solvents. We then incorporated the stability of the hydronium ion into a correlative model for the acid-catalyzed conversion of 1,2-propanediol to propanal. The distinction between these organic solvents can be used to predict the preference of the hydronium ion for specific regions in aqueous mixtures of organic solvents. By measuring the free energy for transferring a hydronium ion from pure water to pure organic solvent, we found that the hydronium ion is destabilized in DIOX, THF, and GVL and stabilized in NMP, ACE, and DMSO relative to water. In this work, classical molecular dynamics simulations were performed to quantify the stability of hydronium and chloride ions by measuring their solvation free energies in water, 1,4-dioxane (DIOX), tetrahydrofuran (THF), γ-valerolactone (GVL), N-methyl-2-pyrrolidone (NMP), acetone (ACE), and dimethyl sulfoxide (DMSO). The solution-phase stability of the hydronium ion catalyst significantly affects the rates of acid-catalyzed reactions, which are ubiquitously utilized to convert biomass to valuable chemicals. Department of Chemical and Biological Engineering, University of Wisconsin – Madison, Madison, WI, United States.
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