Deep eutectic solvents (DESs) are an emerging class of mixtures characterized by significant depressions in melting points compared to those of the neat constituent components. These materials are promising for applications as inexpensive "designer" solvents exhibiting a host of tunable physicochemical properties. A detailed review of the current literature reveals the lack of predictive understanding of the microscopic mechanisms that govern the structure-property relationships in this class of solvents. Complex hydrogen bonding is postulated as the root cause of their melting point depressions and physicochemical properties; to understand these hydrogen bonded networks, it is imperative to study these systems as dynamic entities using both simulations and experiments. This review emphasizes recent research efforts in order to elucidate the next steps needed to develop a fundamental framework needed for a deeper understanding of DESs. It covers recent developments in DES research, frames outstanding scientific questions, and identifies promising research thrusts aligned with the advancement of the field toward predictive models and fundamental understanding of these solvents.

Deep Eutectic Solvents: A Review of Fundamentals and Applications.

From lignin to valuable products–strategies, challenges, and prospects

Current perspective on pretreatment technologies using lignocellulosic biomass: An emerging biorefinery concept

Natural deep eutectic solvents for lignocellulosic biomass pretreatment: Recent developments, challenges and novel opportunities.

Ionic liquids (ILs) and deep eutectic solvents (DESs) have been suggested as eco-friendly alternatives to organic solvents. A trace amount of water is often unavoidable as impurity, and water is also added on purpose to reduce their problematically high viscosity and lower their high price. Understanding the distinct effects of water on the properties of ILs/DESs is highly important. In this review, we collect published experimental and theoretical results for IL/DES–H2O systems at varied water concentrations and analyze them. Results from mechanistic studies, thermodynamic modelling and advanced experiments are collected and critically discussed. Six commonly studied IL/DES–H2O systems were selected to map experimental observations onto microscopic results obtained in mechanistic studies. A great variety of distinct contours of the excess properties can be observed over the entire compositional range, indicating that the properties of IL/DES–H2O systems are highly unpredictable. Mechanistic studies clearly demonstrate that the added H2O rapidly changes the heterogeneous 3D structures of pure ILs/DESs, leading to very different properties and behaviour. There are similarities between aqueous electrolytes and IL/DES solutions but the bulky and asymmetric organic cations in ILs/DESs do not conform to the standard salt dissolution and hydration concepts. Thermodynamic modelling previously assumes ILs/DESs to be either a neutral ion-pair or completely dissociated ions, neglecting specific ion hydration effects. A new conceptual framework is suggested for thermodynamic modelling of IL/DES–H2O binary systems to enable new technologies for their practical applications.

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The peculiar effect of water on ionic liquids and deep eutectic solvents

High reliance on crude oil for energy consumption results in the urgent need to explore and develop alternative renewable sources. One of the most promising routes is the transformation of biomass into biofuels and chemicals. The introduction of deep eutectic solvents in 2004 received a considerable amount of attention across different research fields, particularly in biomass processing. The effectiveness of deep eutectic solvents in breaking down the recalcitrant structure in biomass highlights its impact on the transformation of biomass into various value-added products. In addition, deep eutectic solvents are widely regarded as promising “green” solvents due to their low cost, low toxicity, and biodegradable properties. In this paper, some background information on lignocellulosic biomass and deep eutectic solvents is given. Furthermore, the roles of deep eutectic solvents in biomass processing are discussed, focusing on the impacts of deep eutectic solvents on the selectivity of chemical processes and dissolution of biomass. This review also highlights the advantages and limitations of deep eutectic solvents associated with their usage in biomass valorization.

Potential use of deep eutectic solvents to facilitate lignocellulosic biomass utilization and conversion

Deep eutectic solvent and inorganic salt pretreatment of lignocellulosic biomass for improving xylose recovery.

With the depletion of crude oil reserves, the ever-increasing global energy consumption encourages the efforts to find alternative renewable sources for production of biofuels and value-added chemicals. The conversions of lignocellulosic biomass into biofuels and commodity chemicals via the biotechnological pathway have been the recent trend. Specifically, these products can be obtained through fermentation of reducing sugars, which are the main but basic derivatives from the biomass. In order to overcome the recalcitrant structure of the biomass for effective reducing sugar recovery, a pretreatment stage is normally required. Currently, one of the most novel forms of biomass pretreatment is using energy irradiation methods such as electron beam, gamma ray, pulsed electrical field, microwave and ultrasound. In general, these technologies are often used together with other more conventional chemical and/or biological pretreatment techniques for enhancing sugar recovery. Nevertheless, energy irradiation offers significant improvement in terms of possible cost reduction opportunities and reduced toxicity. Hence, this review highlights the recent studies of using energy irradiation for pretreating biomass as well as the industrial applications of reducing sugars in biotechnological, chemical and fuel sectors. In short, more research needs to be done at the scientific, engineering and economic levels to make energy irradiation one of the front runners in the field of biomass pretreatment.

Ge Hoa Yang

Papers

Potential use of deep eutectic solvents to facilitate lignocellulosic biomass utilization and conversion

Deep eutectic solvent and inorganic salt pretreatment of lignocellulosic biomass for improving xylose recovery.

Role of energy irradiation in aiding pretreatment of lignocellulosic biomass for improving reducing sugar recovery