Search Results (30)

Ternary choline chloride-based deep eutectic solvents (TDESs) exhibit unique physicochemical properties, including lower viscosities, lower melting points, higher thermal stabilities, and enhanced solvations compared to binary deep eutectic solvents (BDESs). Although BDESs have been widely studied, the addition of a third component in TDESs offers opportunities to further optimize their performance. This review aims to evaluate the physicochemical properties of TDESs and highlight their potential applications in sustainable industrial processes compared to BDESs. A comprehensive analysis of the existing literature was conducted, focusing on TDES properties, such as phase behavior, density, viscosity, pH, conductivity, and the effect of water, along with their applications in various fields. TDESs demonstrated superior physicochemical characteristics compared to BDESs, including improved solvation and thermal stability. Their applications in biomass conversion, CO₂ capture, heavy oil upgrading, refrigeration gases, and as solvents/catalysts in organic reactions show significant promise for enhancing process efficiency and sustainability. Despite their advantages, TDESs face challenges including limited predictive models, potential instability under certain conditions, and scalability hurdles. Overall, TDESs offer significant potential for advancing sustainable and efficient chemical processes for industrial applications. Full article

Lithium-ion batteries (LiBs) are utilized in numerous applications due to advancements in technology, and the recovery of end-of-life (EoL) LiBs is imperative for environmental and economic reasons. Pyrometallurgical and hydrometallurgical methods have been used in the recovery of metals such as Li, Co, and Ni in the EoL LiBs. Hydrometallurgical methods, which have been demonstrated to exhibit higher recovery efficiency and reduced energy consumption, have garnered increased attention in recent research. Inorganic acids, including HCl, HNO₃, and H₂SO₄, as well as organic acids such as acetic acid and citric acid, are employed in the hydrometallurgical recovery of these metals. It is imperative to acknowledge the environmental hazards posed by these acids. Consequently, solvometallurgical processes, which involve the use of organic solvents with minimal or no water, are gaining increasing attention as alternative or complementary techniques to conventional hydrometallurgical processes. In the context of solvent systems that have been examined for a range of solvometallurgical methods, deep eutectic solvents (DESs) have garnered particular interest due to their low toxicity, biodegradable nature, tunable properties, and efficient metal recovery potential. In this study, the leaching process of black mass containing graphite, LCO, NMC, and LMO was carried out in a short time using the ternary DES system. The ternary DES system consists of choline chloride (ChCl), glycolic acid (GLY), and ascorbic acid (AA). As a result of the leaching process of cathode powders in the black mass without any pre-enrichment process, Li, Co, Ni, and Mn elements passed into solution with an efficiency of over 95% at 60 °C and within 1 h. Moreover, the kinetics of the leaching process was investigated, and Density Functional Theory (DFT) calculations were used to explain the leaching mechanism. Full article

The rapid growth in lithium-ion battery (LIB) demand has underscored the urgent need for sustainable recycling methods to recover critical metals such as lithium, cobalt, nickel, and manganese. Traditional pyrometallurgical and hydrometallurgical approaches often suffer from high energy consumption, environmental impact, and limited metal selectivity. As an emerging alternative, solvometallurgy, and in particular the use of low-melting mixtures solvents, including deep eutectic solvents, offers a low-temperature, tunable, and potentially more environmentally compatible pathway for black mass processing. This review presents a comprehensive assessment of the recent advances (2020–2025) in the application of LoMMSs for metal recovery from LCO and NCM cathodes, analyzing 71 reported systems across binary, ternary, hydrated, and non-ChCl-based solvent families. Extraction efficiencies, reaction kinetics, coordination mechanisms, and solvent recyclability are critically evaluated, highlighting how solvent structure influences performance and selectivity. Particular attention is given to the challenges of lithium recovery, solvent degradation, and environmental trade-offs such as energy usage, waste generation, and chemical stability. A comparative synthesis identifies the most promising systems based on their mechanistic behavior and industrial relevance. The future outlook emphasizes the need for greener formulations, enhanced lithium selectivity, and life-cycle integration to support circular economy goals in battery recycling. Full article

This study investigates the synthesis and evaluation of ZnO/g-C₃N₄ composites as efficient green catalysts for advanced oxidation processes (AOPs) targeting the treatment of contaminated water. The composites were synthesized using a ternary deep eutectic solvent and physically–chemically characterized in detail, confirming their structural integrity and successful synthesis. Photocatalytic, photo-Fenton- and electro-Fenton-like experiments were conducted using Rhodamine B as a model contaminant to evaluate the catalytic performance, reuse and stability of the synthesized material. The synthesized ZnO/g-C₃N₄ composites demonstrated excellent photocatalytic activity under LED light (395 nm), achieving a pollutant removal of around 59% in 90 min. The combined effect of the designed catalyst and Fenton-like process, a photo-Fenton-like process, significantly improved this performance, achieving removal of close to 95% in 60 min due to the synergistic effects of the irradiation and H₂O₂ activation. Finally, the catalytic action of synthesized ZnO/g-C₃N₄ composites in the electro-Fenton-like process exhibited superior efficiency, achieving 90% removal within 45 min and kinetic constants four times higher than those of anodic oxidation alone. In addition, reuse studies confirmed the stability and catalytic activity of the composites for several cycles with high removal efficiencies, demonstrating their viability for long-term and scalable water treatment applications. These findings highlight the potential of ZnO/g-C₃N₄ composites synthesized through DES as a sustainable and cost-effective alternative for water remediation technologies. Full article

Natural deep eutectic solvents (NADESs) are a sustainable, green option for extraction and reaction media in biorefineries and various chemical and biotechnological applications. Particularly, enzymatic reactions profit from NADES applications, as these solvents help to maintain high substrate solubility while improving both enzyme stability and efficiency. Recent studies confirmed that NADESs can perform multiple functions simultaneously, as reaction media for biocatalytic conversions, but also as substrates and catalysts for reactions, fulfilling the role of a reactive solvent. This study reports the beneficial effect of designed reactive natural deep eutectic solvents (R-NADESs) on the esterification activity and thermal stability of free and immobilized lipases in the synthesis of polyol- and carbohydrate-based biosurfactants. We manufactured and characterized 16 binary and ternary R-NADES systems with choline chloride (ChCl) as the hydrogen bond acceptor (HBA) and carbohydrate polyols; mono-, di-, and oligosaccharides; urea (U); N-methyl urea (MU); and water as the hydrogen bond donors (HBDs), in different combinations and molar ratios, most of which are reported for the first time in this paper. We determined their physicochemical, thermal, and molecular properties, including among others viscosity, polarizability, and the number of hydrogen bonds, and we showed that these properties are controlled by composition, molar ratio, molecular properties, temperature, and water content. Many lipases, both native and immobilized, showed high stability and remarkable catalytic performance in R-NADESs during esterification reactions. Full article

As an environment-friendly biodegradable material, poly (vinyl alcohol) (PVA) has been focused on improving performance and expanding its applications. In this study, improved performance lignin nanoparticle/PVA composite film was prepared by phenolation of bagasse lignin (BL) using a novel ternary deep eutectic solvent (DES). The effects of introduction of DES-phenolated lignin (DL) nanoparticles with different additions (1, 3, 5, 10 wt%) on the properties of DL/PVA composite film were comprehensively studied by mechanical performance test, UV-shielding performance test, contact angle measurement, thermogravimetric analyses and DPPH free radical scavenging activity. The experimental results indicated that lignin nanoparticles (LNPs) were homogeneously distributed in a biodegradable PVA matrix due to hydrogen bonds between the PVA matrix and lignin nanoparticles. With the introduction of DES pretreatment on native bagasse lignin, the various performances of DL/PVA composite films, such as tensile strength, surface hydrophobicity, UV-shielding and thermal stability, were enhanced in comparison with both pure PVA film and BL/PVA composite film incorporated with DES-untreated BL. The tensile strength of DL/PVA composite film with 3 wt% addition increased to 97.79 MPa from 69.41 MPa for pure PVA film, and the water contact angle increased from 43.7° to 84.2°. DL/PVA composite film with 10 wt% addition shielded 95.8% of the UV spectrum (400–200 nm). Moreover, after incorporating the DL nanoparticles into the PVA matrix, the as-obtained DL/PVA composite films displayed good antioxidant activity by eliminating most of the DPPH free radicals. With 10 wt% addition of DL nanoparticles, the DPPH radical scavenging activity of DL/PVA composite film increased by about 76% compared with pure PVA film. These enhanced properties were attributed to the more phenolic hydroxyl groups of DL nanoparticles than of BL and the hydrogen-bonding interactions. In conclusion, the DES-phenolation pretreatment of lignin clearly improved the properties of PVA composite films. Furthermore, as both lignin and PVA are biodegradable, the lignin nanoparticle/PVA composite film may be a promising candidate for fully biodegradable robust coating materials with vital potential applications, such as UV-shielding and food packaging, etc. Full article

Anthocyanins are amazing plant-derived colorants with highly valuable properties; however, their chemical and color instability issues limit their wide application in different food industry-related products such as active and intelligent packaging. In a previous study, it was demonstrated that anthocyanins could be stabilized into green plasticizers namely deep eutectic solvents (DESs). In this work, the fabrication of edible films by integrating anthocyanins along with DESs into biocompatible chitosan (CHT)-based formulations enriched with polyvinyl alcohol (PVA) and PVA nanoparticles was investigated. CHT/PVA-DES films’ physical properties were characterized by scanning electron microscopy, water vapor permeability, swelling index, moisture sorption isotherm, and thermogravimetry analysis. Innovative red-to-blue formulation films were achieved for CHT/PVA nanoparticles (for 5 min of sonication) at a molar ratio 1:1, and with 10% of ternary DES (TDES)-containing malvidin-3-glucoside (0.1%) where the physical properties of films were enhanced. After immersion in solutions at different pH values, films submitted to pHs 5–8 were revealed to be more color stable and resistant with time than at acidic pH values. Full article

Solubility is not only a crucial physicochemical property for laboratory practice but also provides valuable insight into the mechanism of saturated system organization, as a measure of the interplay between various intermolecular interactions. The importance of these data cannot be overstated, particularly when dealing with active pharmaceutical ingredients (APIs), such as dapsone. It is a commonly used anti-inflammatory and antimicrobial agent. However, its low solubility hampers its efficient applications. In this project, deep eutectic solvents (DESs) were used as solubilizing agents for dapsone as an alternative to traditional solvents. DESs were composed of choline chloride and one of six polyols. Additionally, water–DES mixtures were studied as a type of ternary solvents. The solubility of dapsone in these systems was determined spectrophotometrically. This study also analyzed the intermolecular interactions, not only in the studied eutectic systems, but also in a wide range of systems found in the literature, determined using the COSMO-RS framework. The intermolecular interactions were quantified as affinity values, which correspond to the Gibbs free energy of pair formation of dapsone molecules with constituents of regular solvents and choline chloride-based deep eutectic solvents. The patterns of solute–solute, solute–solvent, and solvent–solvent interactions that affect solubility were recognized using Orange data mining software (version 3.36.2). Finally, the computed affinity values were used to provide useful descriptors for machine learning purposes. The impact of intermolecular interactions on dapsone solubility in neat solvents, binary organic solvent mixtures, and deep eutectic solvents was analyzed and highlighted, underscoring the crucial role of dapsone self-association and providing valuable insights into complex solubility phenomena. Also the importance of solvent–solvent diversity was highlighted as a factor determining dapsone solubility. The Non-Linear Support Vector Regression (NuSVR) model, in conjunction with unique molecular descriptors, revealed exceptional predictive accuracy. Overall, this study underscores the potency of computed molecular characteristics and machine learning models in unraveling complex molecular interactions, thereby advancing our understanding of solubility phenomena within the scientific community. Full article

Rosehips are processed and consumed in numerous forms, such as juice, wine, herbal tea, yogurt, preserved fruit, and canned products. The seeds share in fruit is 30–35% and they have recently been recognized as an important source of oil rich in unsaturated fatty acids. However, after defatting, seed waste may still contain some polar polyphenolic compounds, which have been scarcely investigated. The aim of this study was to examine the potential of the defatted seed waste as a source of polyphenols. For the defatting process, supercritical carbon dioxide extraction at 300 bar and 40 °C was applied. The capacity of eight different natural deep eutectic solvents (NADES) for the recovery of phenolics from defatted rosehip seed powder (dRSP) was examined. In the extracts obtained with ultrasound-assisted NADES extraction, twenty-one phenolic compounds were identified with LC-MS/MS, among which the most abundant were quinic acid (22.43 × 10³ µg/g dRSP) and catechin (571.93 µg/g dRSP). Ternary NADES formulations based on lactic acid proved to be superior. Potential correlations between identified chemical compounds, solvent polarity and viscosity, as well as the compound distributions across studied solvent combinations in PCA hyperspace, were also investigated. PCA demonstrated that more polar NADES mixtures showed improved extraction potential. The established environmentally friendly process represents an approach of transforming rosehip seed waste into value-added products with the potential to be applied in the food industry and to contribute to sustainable production. Full article

Research on metal salt-based deep eutectic solvent (DES) pretreatment is still in its infancy, and the effect of hydroxyl groups on Cl⁻ in choline chloride (ChCl) is not resolved. In this study, a type IV DES composed of metal salt and glycerol (Gly) was prepared for pretreatment of moso bamboo to improve its enzymatic hydrolysis. The correlation between enzymatic hydrolysis and the contents of hemicelluloses and lignin was evaluated using the Box–Behnken design. The results showed that FeCl₃-based DES was optimal among various DES. The solid recovery was reduced to 55.54% following FeCl₃/Gly pretreatment, which was effective in the removal of hemicelluloses and lignin compared with ternary DES pretreatment (with ChCl) under mild conditions (100 °C, 3 h). With the increase of pretreatment temperature (120 °C, 2 h), a significant proportion of hemicelluloses (76.07%) and lignin (62.77%) was removed. The structure of FeCl₃/Gly pretreatment residue was seriously damaged, and the glucose yield increased to 91.13% following enzymatic hydrolysis. This correlation indicated that the hemicelluloses’ content had a significant influence on enzymatic hydrolysis of the residue following FeCl₃/Gly pretreatment. This study elucidates the pretreatment effect of metal salt-based DES, which will be helpful in the value-added conversion of moso bamboo under mild conditions. Full article

The molecular weight of lignin extracted from lignocellulosic biomass is an important factor in determining its valorization in industrial processes. Herein, this work aims to explore the extraction of high molecular weight and bioactive lignin from water chestnut shells under mild conditions. Five kinds of deep eutectic solvents were prepared and applied to isolate lignin from water chestnut shells. The extracted lignin was further characterized with element analysis, gel permeation chromatography, and Ultraviolet-visible and Fourier-transform infrared spectroscopy. The distribution of pyrolysis products was identified and quantified with thermogravimetric analysis—Fourier-transform infrared spectroscopy and pyrolysis-gas chromatograph-mass spectrometry. The results showed that choline chloride/ethylene glycol/p-toluenesulfonic acid (1:1.8:0.2 molar ratio) exhibited the highest fractionation efficiency for lignin (84.17% yield) at 100 °C for 2 h. Simultaneously, the lignin showed high purity (90.4%), high relative molecular weight (37,077 g/mol), and excellent uniformity. Furthermore, the aromatic ring structure of lignin remained intact, consisting mainly of p-hydroxyphenyl, syringl, and guaiacyl subunits. The lignin generated a large number of volatile organic compounds during the depolymerization process, mainly composed of ketones, phenols, syringols, guaiacols, esters, and aromatic compounds. Finally, the antioxidant activity of the lignin sample was evaluated with the 1,1-diphenyl-2-picrylhydrazyl radical scavenging assay; the lignin from water chestnut shells showed excellent antioxidant activity. These findings confirm that lignin from water chestnut shells has a broad application prospect in valuable chemicals, biofuels and bio-functional materials. Full article

The efficient biosynthesis of chiral amines at an industrial scale to meet the high demand from industries that require chiral amines as precursors is challenging due to the poor stability and low catalytic efficiency of ω-transaminases (ω-TAs). Herein, this study adopted a green and efficient solvent engineering method to explore the effects of various aqueous solutions of deep eutectic solvents (DESs) as cosolvents on the catalytic efficiency and stability of ω-TA. Binary- and ternary-based DESs were used as cosolvents in enhancing the catalytic activity and stability of a ω-TA variant from Aspergillus terreus (E133A). The enzyme exhibited a higher catalytic activity in a ternary-based DES that was 2.4-fold higher than in conventional buffer. Moreover, the thermal stability was enhanced by a magnitude of 2.7, with an improvement in storage stability. Molecular docking studies illustrated that the most potent DES established strong hydrogen bond interactions with the enzyme’s amino acid, which enhanced the catalytic efficiency and improved the stability of the ω-TA. Molecular docking is essential in designing DESs for a specific enzyme. Full article

The conversion of lignocellulose into valuable chemicals has been recognized as the key technology in green chemistry. However, selective degradation of hemicellulose and cellulose with the production of lignin is still a challenge. Therefore, a two-step process has been developed to degrade corncob into xylose and glucose under mild conditions. At first, the corncob was treated with the lower concentration of zinc chloride aqueous solution (30–55 w%) at 95 °C with a short reaction time (8–12 min) and 30.4 w% (selectivity = 89%) of xylose obtained with a solid residue of the composite of cellulose and lignin. Next, the solid residue was treated with a high concentration of zinc chloride aqueous solution (65–85 w%) at 95 °C for about 10 min, and 29.4 w% (selectivity = 92%) of glucose can be obtained. Combining the two steps, the total yield of xylose is 97%, while glucose is 95%. In addition, high pure lignin can be obtained simultaneously, which was confirmed using HSQC studies. Furthermore, for the solid residue of the first-step reaction, a ternary deep eutectic solvent (DES) (choline chloride/oxalic acid/1,4-butanediol, ChCl/OA/BD) has been used to separate the cellulose and lignin efficiently, and high-quality cellulose (Re-C) and lignin (Re-L) were obtained. Furthermore, it provides a simple method to disassemble the lignocellulose for monosaccharides, lignin, and cellulose. Full article

The aim of the study was to prepare and characterize composite materials based on thermoplastic starch (TPS)/deep eutectic solvent (DES). Potato starch was plasticized with ternary DES: urea:glycerol:sorbitol and modified with the selected fillers: microcrystalline cellulose and sodium montmorillonite. Films were prepared via twin-screw extrusion and thermocompression of the extrudates. Then, the physicochemical properties of the TPS films were examined. The ternary DES effectively plasticized the polysaccharide leading to a highly amorphous structure of the TPS (confirmed via mechanical tests, DMTA and XRD analyses). An investigation of the behavior in water (swelling and dissolution degree) and water vapor transmission rate of the films was determined. The introduction of the two types of fillers resulted in higher tensile strength and better barrier properties of the composite TPS films. However, montmorillonite addition exhibited a higher impact than microcrystalline cellulose. Moreover, a cone calorimetry analysis of the TPS materials revealed that they showed better fire-retardant properties than TPS plasticized with a conventional plasticizer (glycerol). Full article

The separation of aromatic/olefin mixtures is a difficult task in the petrochemical industry, since the boiling points of these hydrocarbons are very similar. This work aims to use deep eutectic solvents (DESs) for the extraction of toluene from 1-hexene by liquid–liquid extraction. A total of 53 DESs were studied qualitatively and quantitatively using the COSMO-RS approach to separate the binary mixture of toluene and 1-hexene. The selectivity, capacity, and performance index of all DESs were evaluated by calculating the activity coefficient at infinite dilution. The σ-profile and σ-potential of each component were interpreted to evaluate the interactions between the different species. We then selected three DESs for experimental validation, namely benzyltriphenylphosphonium chloride:triethylene glycol BzTPPCl:TEG (1:8), tetrabutylammonium bromide:triethylene glycol TBABr:TEG (1:3), and tetrabutylammonium bromide:ethylene glycol TBABr: EG (1:4). Experimental liquid–liquid equilibrium data were obtained for the ternary mixtures {1-hexene (1) + toluene (2) + DES (3)} at T = 298.15 K and atmospheric pressure. Based on the selectivity data and the solute distribution ratio, the feasibility of different DESs as extractive solvents was tested. Finally, ¹H NMR was performed to elucidate the extraction mechanism. No DES was found in the raffinate phase, indicating minimal cross-contamination. Full article