Aqueous Ionic Liquids and Deep Eutectic Solvents for Cellulosic Biomass Pretreatment and Saccharification

Ionic liquids (ILs) have proven effective solvents for pretreating lignocellulose, leading to the fast saccharification of cellulose and hemicellulose. However, the high current cost of most ILs remains a major barrier to commercializing this recent approach at a practical scale. As a strategic detour, aqueous solutions of ILs are also being explored as less costly alternatives to neat ILs for cellulose pretreatment. However, limited studies on a few select IL systems are known and there remains no systematic survey of various ILs, eluding an in-depth understanding of pretreatment mechanisms afforded by aqueous IL systems. As a step toward filling this gap, this study presents results for Avicel cellulose pretreatment by neat and aqueous solutions (1.0 and 2.0 M) of 20 different ILs and three deep eutectic solvents, correlating enzymatic hydrolysis rates of pretreated cellulose with various IL properties such as hydrogen-bond basicity, polarity, Hofmeister ranking, and hydrophobicity. The pretreatment efficiencies of neat ILs may be loosely correlated to the hydrogen-bond basicity of the constituent anion and IL polarity; however, the pretreatment efficacies for aqueous ILs are more complicated and cannot be simply related to any single IL property. Several aqueous IL systems have been identified as effective alternatives to neat ILs in lignocellulose pretreatment. In particular, this study reveals that aqueous solutions of 1-butyl-3-methylimidazolium methanesulfonate ([BMIM][MeSO₃]) are effective for pretreating switchgrass (Panicum virgatum), resulting in fast saccharification of both cellulose and hemicellulose. An integrated analysis afforded by X-ray diffraction, scanning electron microscopy, thermogravimetric analysis and cellulase adsorption isotherm of lignocellulose samples is further used to deliver a more complete view of the structural changes attending aqueous IL pretreatment.