Glycerol-based deep eutectic solvents: Physical properties
TL;DR: In this paper, 70 DESs were synthesized successfully based on glycerol (Gly) as the HBD with different phosphonium and ammonium salts, namely methyl triphenyl phosphono-bromide (MTPB), benzyl triphenyi-triphenyl-phosphonium bromide(BTPC), allyl triphethenyl phono-phonium (ATPB), choline chloride (ChCl), N,N-diethylethanolammonium chloride (DAC), and tetra-
About: This article is published in Journal of Molecular Liquids.The article was published on 2013-02-01. It has received 353 citations till now. The article focuses on the topics: Phosphonium & Deep eutectic solvent.
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TL;DR: This Review considers several aspects of the most prominent sustainable organicsolvents in use today, ionic liquids, deep eutectic solvents, supercritical fluids, switchable solVents, liquid polymers, and renewable solvent, giving a more complete picture of the current status of sustainable solvent research and development.
Abstract: Sustainable solvents are a topic of growing interest in both the research community and the chemical industry due to a growing awareness of the impact of solvents on pollution, energy usage, and contributions to air quality and climate change. Solvent losses represent a major portion of organic pollution, and solvent removal represents a large proportion of process energy consumption. To counter these issues, a range of greener or more sustainable solvents have been proposed and developed over the past three decades. Much of the focus has been on the environmental credentials of the solvent itself, although how a substance is deployed is as important to sustainability as what it is made from. In this Review, we consider several aspects of the most prominent sustainable organic solvents in use today, ionic liquids, deep eutectic solvents, supercritical fluids, switchable solvents, liquid polymers, and renewable solvents. We examine not only the performance of each class of solvent within the context of the...
1,051 citations
TL;DR: A detailed review of the current literature reveals the lack of predictive understanding of the microscopic mechanisms that govern the structure-property relationships in deep eutectic solvents, and highlights recent research efforts to elucidate the next steps needed to develop a fundamental framework needed for a deeper understanding.
Abstract: 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.
911 citations
TL;DR: Deep eutectic solvents (DESs) have been considered as alternatives to ILs that maintain most of their relevant properties, such as task-specific character, and at the same time avoid some of their problems, mainly from economic and environmental viewpoints as discussed by the authors.
Abstract: Sustainable technologies applied to energy-related applications should develop a pivotal role in the next decades. In particular, carbon dioxide capture from flue gases emitted by fossil-fueled power plants should play a pivotal role in controlling and reducing the greenhouse effect. Therefore, the development of new materials for carbon capture purposes has merged as central research line, for which many alternatives have been proposed. Ionic liquids (ILs) have emerged as one of the most promising choices for carbon capture, but in spite of their promising properties, some serious drawbacks have also appeared. Deep eutectic solvents (DESs) have recently been considered as alternatives to ILs that maintain most of their relevant properties, such as task-specific character, and at the same time avoid some of their problems, mainly from economic and environmental viewpoints. DES production from low-cost and natural sources, together with their almost null toxicity and total biodegradability, makes these sol...
719 citations
TL;DR: In this article, a stricter definition of a deep eutectic solvent (DES) is proposed, for which the point temperature should be lower than that of an ideal liquid mixture, and hydrogen bonding between the DES components should not be used to define or characterize a DES.
Abstract: A stricter definition of a deep eutectic solvent (DES) is urgent, so that it may become a sound basis for further developments in this field. This communication aims at contributing to deepening the understanding of eutectic and deep eutectic mixtures concerning their definition, thermodynamic nature and modelling. The glut of literature on DES applications should be followed by a similar effort to address the fundamental questions on their nature. This hopefully would contribute to correct some widespread misconceptions, and help to establish a stringent definition of what a DES is. DES are eutectic mixtures for which the eutectic point temperature should be lower to that of an ideal liquid mixture. To identify and characterize them, their phase diagrams should be known, in order to compare the real temperature depression to that predicted if ideality is assumed, and to define composition ranges for which they are in the liquid state at operating temperatures. It is also shown that hydrogen bonding between the DES components should not be used to define or characterize a DES, since this would describe many ideal mixtures. The future of deep eutectic solvents is quite promising, and we expect that this work will contribute to the efficient design and selection of the best DES for a given application, and to model properties and phase equilibria without which the process design is impractical.
508 citations
TL;DR: Results on phytotoxicity imply that tested DESs are non-toxic with seed germination EC50 values higher than 5000 mg L(-1) and classified as'readily biodegradable' based on their high levels of mineralization.
448 citations
References
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TL;DR: There have been parallel and collaborative exchanges between academic research and industrial developments since the materials were first reported in 1914, it is demonstrated.
Abstract: In contrast to a recently expressed, and widely cited, view that “Ionic liquids are starting to leave academic labs and find their way into a wide variety of industrial applications”, we demonstrate in this critical review that there have been parallel and collaborative exchanges between academic research and industrial developments since the materials were first reported in 1914 (148 references)
4,865 citations
3,909 citations
TL;DR: Eutectic mixtures of urea and a range of quaternary ammonium salts are liquid at ambient temperatures and have interesting solvent properties.
3,550 citations
Book•
01 Jan 2002
TL;DR: The early years of Ionic liquid production were covered in this article, where a new generation of soluble supports for Supported Organic Synthesis (SPOS) was proposed. But this support was not applied to the task-specific Ionic liquids.
Abstract: Preface A Note From The Editors THE EARLY YEARS OF IONIC LIQUIDS SYNTHESIS AND PURIFICATION Synthesis Quality Aspects and other Questions Related to Commercial Ionic Liquid Production Synthesis of Task-specific Ionic Liquids PHYSICO-CHEMICAL PROPERTIES Melting Points Viscosity and Density Solubility and Solvation in Ionic Liquids Gas Solubilities Polarity Electrochemistry STRUCTURE AND DYNAMICS Order in the Liquid State and Structure Computational Modelling of Ionic Liquids Translational Diffusion Molecular Reorientational Dynamics ORGANIC SYNTHESIS Ionic Liquids in Organic Synthesis: Effects on Rate and Selectivity Stoicheiometric Organic Reactions and Acid-catalysed Reactions in Ionic Liquids Transition Metal Catalysis in Ionic Liquids Ionic Liquids in Multiphasic Reactions Task Specific Ionic Liquids (TSILs): A New Generation of Soluble Supports for Supported Organic Synthesis (SPOS) Supported Ionic Liquid Phase Catalysts Multiphasic Catalysis Using Ionic Liquids in Combination with Compressed CO2 INORGANIC SYNTHESIS Directed Inorganic and Organometallic Synthesis Making of Inorganic Materials by Electrochemical Methods Ionic Liquids in Material Synthesis: Functional Nanoparticles and Other Inorganic Nanostructures POLYMER SYNTHESIS IN IONIC LIQUIDS BIOCATALYTIC REACTIONS IN IONIC LIQUIDS INDUSTRIAL APPLICATIONS OF IONIC LIQUIDS CONLUDING REMARKS AND OUTLOOK
3,423 citations
TL;DR: All works discussed in this review aim at demonstrating that Deep Eutectic Solvents not only allow the design of eco-efficient processes but also open a straightforward access to new chemicals and materials.
Abstract: Within the framework of green chemistry, solvents occupy a strategic place. To be qualified as a green medium, these solvents have to meet different criteria such as availability, non-toxicity, biodegradability, recyclability, flammability, and low price among others. Up to now, the number of available green solvents are rather limited. Here we wish to discuss a new family of ionic fluids, so-called Deep Eutectic Solvents (DES), that are now rapidly emerging in the current literature. A DES is a fluid generally composed of two or three cheap and safe components that are capable of self-association, often through hydrogen bond interactions, to form a eutectic mixture with a melting point lower than that of each individual component. DESs are generally liquid at temperatures lower than 100 °C. These DESs exhibit similar physico-chemical properties to the traditionally used ionic liquids, while being much cheaper and environmentally friendlier. Owing to these remarkable advantages, DESs are now of growing interest in many fields of research. In this review, we report the major contributions of DESs in catalysis, organic synthesis, dissolution and extraction processes, electrochemistry and material chemistry. All works discussed in this review aim at demonstrating that DESs not only allow the design of eco-efficient processes but also open a straightforward access to new chemicals and materials.
3,325 citations