The use of organic solvents in biomass conversion reactions can lead to high rates and improved selectivities. Here, we elucidate the effects of organic solvent mixtures with water on the kinetics of acid-catalysed dehydration reactions of relevance to biomass conversion. Based on results from reaction kinetics studies, combined with classical and ab initio molecular dynamics simulations, we show that the rates of acid-catalysed reactions in the liquid phase can be enhanced by altering the extents of solvation of the initial and transition states of these catalytic processes. The extent of these effects increases as the number of vicinal hydroxyl or oxygen-containing groups in the reactant increases, moving from an alcohol (butanol), to a diol (1,2-propanediol), to a carbohydrate (fructose). We demonstrate that the understanding of these solvation effects can be employed to optimize the rate and selectivity for production of the biomass platform molecule hydroxymethylfurfural from fructose.

在生物质转化反应中使用有机溶剂可导致较高的转化率和更高的选择性。在这里，我们阐明了有机溶剂与水的混合物对与生物质转化有关的酸催化脱水反应动力学的影响。基于反应动力学研究的结果，结合经典的和从头算的分子动力学模拟，我们表明，可以通过改变这些催化反应的初始和过渡态的溶剂化程度来提高液相中酸催化的反应速率流程。这些作用的程度随着反应物中邻羟基或含氧基团数目的增加而增加，从醇（丁醇）转移到二醇（1,2-丙二醇），再转移到碳水化合物（果糖）。