Ternary Deep Eutectic Solvents Research Articles

Binary and Ternary Deep Eutectic Solvents for Methylene Green Electropolymerization on Multiwalled Carbon Nanotubes: Optimization, Characterization and Application.

Choline chloride (ChCl) based binary and ternary deep eutectic solvents (DES) were evaluated for methylene green electropolymerization with oxalic acid (OA) and ethylene glycol (EG) as hydrogen bond donors. Binary DES ChCl : OA in molar ratios 1 : 1 and 2 : 1 and ChCl : EG 1 : 2 and ternary DES (tDES) in different molar ratios and percentages of water were evaluated. The highest polymer growth was in ChCl : OA : EG-tDES with 13% added water, that had a lower viscosity and higher ionic conductivity when associated with HCl as dopant. This enhanced the formation of more cation radicals and, consequently, more polymer formation. The PMG/MWCNT/GCE-tDES sensor was successfully applied to the simultaneous determination of 5-aminosalicylic acid (5-ASA) and acetaminophen (APAP) by differential pulse voltammetry in the concentration range 1 μM-200 μM, with detection limits of 0.37 μM and 0.49 μM for 5-ASA and APAP, respectively. The sensor demonstrated good repeatability, reproducibility and stability, and was successfully applied in pharmaceutical formulations.

Novel ternary deep eutectic solvents pretreatment of corn stalk to realize high-value utilization

The high-valued utilization of biomass components through pretreatment technology can effectively alleviate the pressure of energy and environment. In this study, a ternary deep eutectic solvent (TDES) was prepared by using glycolic acid (GA) and ethylene glycol (EG) as double hydrogen donors and benzyl trimethyl ammonium chloride (TMBAC) as hydrogen acceptor. The corn stalk was separated by TDES to obtain cellulose-rich solid residue and low-condensed lignin. Moreover, the solid residue was converted into bio-oil by rapid pyrolysis, and the low-condensed lignin was converted into fluorescent lignin by grafting luminol for information encryption. The results showed that under the pretreatment condition of 150℃ for 3 h, TDES with the molar ratio of 1:1:2 had a lignin removal ratio of 90.60 %, and the yield of levoglucosan obtained from solid residue pyrolysis bio-oil reached 36.38 %. Furthermore, TDES prevented lignin from forming a C-C polycondensation structure and endowed it with polyhydroxy properties, which was beneficial to graft luminolto enhance the fluorescence intensity efficiently. The high-intensity fluorescent grafted lignin was used for information encryption of various materials. The mechanism of TDES pretreatment and luminol grafting were explored, and the mass balance of corn stalk during pretreatment was described. This study provides a green, environmentally friendly, and efficient pretreatment process for the high-value utilization of biomass.

Machine learning approach for mapping the heat capacity of deep eutectic solvents for sustainable energy applications

This study introduces a breakthrough machine learning (ML) approach to predict the heat capacity of deep eutectic solvents (DESs), an emerging class of environmentally friendly solvents, for sustainable energy applications. Leveraging an extensive dataset of 2,696 data points across 55 DES mixtures with 389 unique compositions, the research significantly extends the scope of previous studies. The methodology employs group contribution-based critical properties to elucidate intricate molecular-level dynamics, enabling the models to decode complex interactions governing DES behavior. The multi-dimensional strategy encompasses conventional binary DESs, ternary DESs, and water + DES mixtures, providing a holistic understanding of these green solvents. The developed artificial neural network (ANN) exhibits exceptional performance, with an R2 value of 0.995 in training and 0.988 in testing, substantially surpassing existing models. Rigorous comparative analysis and applicability domain assessment confirm the robustness and superiority of this approach in predicting heat capacities for diverse DES compositions. Key findings include identifying the molecular factors influencing DES heat capacities, with critical volume, molecular weight, and critical temperature having the greatest impact. An open-source, user-friendly Excel tool based on the ANN model is developed to promote accessibility and practical application in energy and environmental sectors. This work revolutionizes the understanding and prediction of DES thermophysical properties, paving the way for their enhanced utilization in eco-friendly energy systems, thermal management, green materials development, and sustainable fuel processing.

Synergistic ternary deep eutectic solvents: An archetype for sustainable and eco-conscious Li and Co recovery from spent batteries

The development of sustainable materials for energy is a critical challenge in the pursuit of a circular economy. This study presents an innovative approach for recycling lithium-ion batteries (LIBs) using a novel, sustainable deep eutectic solvent (DES) composed of glycine, ascorbic acid, and water. This natural, chloride-free ternary DES leverages the biocompatible and eco-friendly properties of its constituents, achieving exceptional leaching efficiency of 99.1 % for lithium and 97.9 % for cobalt under optimized conditions. A multifaceted methodology integrating advanced factorial design, kinetic modeling, and machine learning was employed to refine the process parameters and enhance leaching efficiency. The extraction kinetics were predominantly governed by endothermic surface reactions, characterized by activation energies of 81.5 kJ/mol for Co and 110.9 kJ/mol for Li. An ensemble neural network model accurately predicted the extraction with an R2 > 0.95, demonstrating the robustness of the computational approach. The DES exhibited excellent recyclability over five cycles, thereby emphasizing its potential for practical industrial applications in the field of sustainable materials management. This approach facilitated the selective recovery of high-purity lithium oxalate and cobalt oxalate, underscoring the efficiency and environmental benefits of the process. DFT calculations provided insights into the extraction mechanism, revealing the crucial role of hydrogen bonding and synergistic effects of the DES components. This pioneering study not only advances LIB recycling but also establishes a comprehensive, quantitatively validated framework, paving the way for future innovations in sustainable materials management and supporting global efforts towards a circular economy in energy storage.

Combining High-Throughput Experiments and Active Learning to Characterize Deep Eutectic Solvents.

The high tunability of deep eutectic solvents (DESs) stems from the ease of changing their precursors and relative compositions. However, measuring the physicochemical properties across large composition and temperature ranges, necessary to properly design target-specific DESs, is tedious and error-prone and represents a bottleneck in the advancement and scalability of DES-based applications. As such, active learning (AL) methodologies based on Gaussian processes (GPs) were developed in this work to minimize the experimental effort necessary to characterize DESs. Owing to its importance for large-scale applications, the reduction of DES viscosity through the addition of a low-molecular-weight solvent was explored as a case study. A high-throughput experimental screening was initially performed on nine different ternary DESs. Then, GPs were successfully trained to predict DES viscosity from its composition and temperature, showcasing the ability of these stochastic, nonparametric models to accurately describe the physicochemical properties of complex mixtures. Finally, the ability of GPs to provide estimates of their own uncertainty was leveraged through an AL framework to minimize the number of data points necessary to obtain accurate viscosity modes. This led to a significant reduction in data requirements, with many systems requiring only five independent viscosity data points to be properly described.

Absorption-Desorption Characteristics of the Synthesized Deep Eutectic Solvents for Carbon Dioxide Capture

The development of an environmentally friendly CO2 absorbent with significant energy utilization which can be an alternative to CO2 capture by an ethanolamine solution is presently an obligatory issue. In this work, binary and ternary deep eutectic solvents (DESs) were prepared according to their CO2 absorption/desorption performances. A series of DESs comprise different hydrogen bonding donor (HBD)- acceptor (HBA) pairs as CO2 capturing solvents; HBAs include choline chloride (ChCl) and tetrabutylammonium bromide (TBAB), and selected amines are represented as HBDs and include monoethanolamine (MEA), diethanolamine (DEA), and triethanolamine (TEA). Binary DESs synthesized of ChCl/MEA, ChCl/DEA, ChCl/TEA, TBAB/MEA, TBAB/DEA, and TBAB/TEA in a CO2 absorption cell at a mole ratio of 1:4. While selected amidines were represented as super-based (SB) and included 1,5-Diazabicyclo [4.3.0] non-5-ene (DBN) and 1,8-Diazabicyclo [5.4.0] undec-7-ene (DBU). The ternary DESs were prepared by adding DBN or DBU to the binary DESs system in a (1:4:3) molar ratio. CO2 absorption experiments were attained at atmospheric pressure and a temperature of 30 °C using 15 vol.% CO2 with 85 vol.% N2. On the other hand, the regeneration process for DESs was conducted at 90 oC. Binary DES synthesized from ChCl/MEA gives a higher absorption rate of CO2 of 0.0177 mole/kg. min, CO2 absorption loading of 2.9092 mole CO2/kg solvent, cyclic loading of 2.0001 mole CO2/kg solvent, and a regeneration efficiency of 68.75%. The synthesis DESs showed a better performance compare with a common Ionic liquids.

Novel ternary deep eutectic solvents used for recycling lithium and cobalt from waste lithium-ion batteries

The escalating disposal of lithium-ion batteries (LIBs) poses significant environmental challenges but also offers substantial opportunities for resource recovery. In this work, we introduce a recycling strategy using a green, cost-effective ternary deep eutectic solvent (DES) composed of guanidine hydrochloride, ethylene glycol, and maleic acid. The DES can achieve >99.5 % leach efficiency of lithium (Li) and cobalt (Co) at 100 °C, 9h, and L/S=50. The kinetic study found that the chemical reaction rate at the interface was the key to controlling the leaching process. The study of leaching mechanisms found that the acidity and coordination ability of DES were the main driving forces of leaching. Co loaded in the DES phase can almost precipitate out by using oxalic acid, achieving the separation of Li and Co. After reusing three times, the maximum load of Li in the DES phase reached 4.1 mg/g. These outstanding performances, along with the avoidance of the use of hazardous chemicals and the reduction of high costs, confirmed that the DES possesses a promising prospect for sustainable, large-scale application in efficiently leaching valuable metals from LiCoO2.

Synthesis of green magnetic molecularly imprinted polymers for selective extraction of rifaximin in milk samples

In this study, a new analytical method was developed using magnetic molecularly imprinted polymers (MMIPs) by employing eco-friendly supramolecular ternary deep eutectic solvents to synthesize these MMIPs for selective extraction of rifaximin. The characterization analysis and adsorption affinity investigation were conducted. The results showed fast adsorption (15 min) with high adsorption capacity (43.20 mg g−1) and selectivity for rifaximin. Various extraction parameters were optimized, achieving recoveries ranging from 86.67% to 99.47% in spiked milk samples using high-performance liquid chromatography (HPLC). The detection and quantification limits were 0.01 mg L−1 and 0.03 mg L−1, respectively. The method exhibited low RSDs (<4.70%) and excellent selectivity, with MMIPs reusable up to seven times with only a 10% performance loss. This study proposes a convenient and reliable method for trace-level rifaximin extraction from milk using eco-friendly MMIPs.

Stabilization of Non-Native Folds and Programmable Protein Gelation in Compositionally Designed Deep Eutectic Solvents.

Proteins are adjustable units from which biomaterials with designed properties can be developed. However, non-native folded states with controlled topologies are hardly accessible in aqueous environments, limiting their prospects as building blocks. Here, we demonstrate the ability of a series of anhydrous deep eutectic solvents (DESs) to precisely control the conformational landscape of proteins. We reveal that systematic variations in the chemical composition of binary and ternary DESs dictate the stabilization of a wide range of conformations, that is, compact globular folds, intermediate folding states, or unfolded chains, as well as controlling their collective behavior. Besides, different conformational states can be visited by simply adjusting the composition of ternary DESs, allowing for the refolding of unfolded states and vice versa. Notably, we show that these intermediates can trigger the formation of supramolecular gels, also known as eutectogels, where their mechanical properties correlate to the folding state of the protein. Given the inherent vulnerability of proteins outside the native fold in aqueous environments, our findings highlight DESs as tailorable solvents capable of stabilizing various non-native conformations on demand through solvent design.

Ternary deep eutectic Solvents-Based Three-Phase partitioning for speciation of Cr (Ⅲ) and Cr (Ⅵ) in edible liquid Oil: A promising method for substituting

In this paper, a novelty ternary deep eutectic solvents was prepared with choline chloride, ethylene glycol and glycerol. The pH value was adjust to develop three-phase for speciation of Cr (Ⅲ) and Cr (Ⅵ) extract and separate in ganoderma lucidum spore oil based on ternary deep eutectic solvents. The results show that DES-4 has a good extraction of Cr (III) and Cr (VI), the sample-extraction ratio was 3:1, Cr (III) was protected by EDTA, all chromium ions in ganoderma lucidum spore oil was extracted by near 100 % in 2 times, Cr (III) and Cr (VI) was well separated by saturated buffer solution of KH2PO4/H3PO4 (pH = 4.5). The LOD is 0.031 mg/kg. The RSD is 4.1 %. The recovery between 85.2 % and 111.5 %. This method was successfully applied to detect speciation chromium in other edible liquid oil.

Chitosan/Polyvinyl Alcohol-Based Biofilms Using Ternary Deep Eutectic Solvents towards Innovative Color-Stabilizing Systems for Anthocyanins.

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.

Cresyl violet electropolymerization on functionalized multiwalled carbon nanotubes in carboxylic acid based ternary deep eutectic solvents for hydroquinone sensing

The phenazine dye cresyl violet (CVio) has been evaluated as precursor for the preparation of a new electrochemical sensor based on poly(cresyl violet) deposited on multiwalled carbon nanotube (CNT) modified glassy carbon electrodes (GCE) in neutralized acid-doped ternary deep eutectic solvents (DES). DES with choline chloride as hydrogen bond acceptor and with different hydrogen bond donors (HBD), namely acetic acid, ethylene glycol and oxalic acid were evaluated for CVio electropolymerization by potential cycling. The best polymer films were obtained in ternary DES with the two HBD acetic acid plus ethylene glycol doped with H2SO4 and followed by NaOH neutralization. Electrochemical characterization (voltammetric and electrochemical impedance) showed the formation of anthraquinone groups during electropolymerization, which is initiated on the CNT by the formation of a cation radical. Anthraquinones in the polymer film led to an increased response at the modified electrode for the determination of hydroquinone (H2Q) with low LOD (0.25 µmol L−1) in a broad linear range (1–80 µmol L−1), with good reproducibility, repeatability, and stability. The sensor was successfully applied to the quantification of H2Q in dermatological creams with no matrix effect towards hydroquinone response.

Investigation of effective CO2 capture by ternary deep eutectic solvents based on superbase

The absorption and separation of CO2 is one of the main strategies to reduce carbon emissions and mitigate global climate change. In this context, a series of ternary superbase/betaine-based deep eutectic solvents (DESs) were synthesized to capture CO2, and their density, viscosity and thermal stability were investigated. The effects of temperature, pressure, different hydrogen bond donors (HBDs) and alkalinity of the superbase on their CO2 affinity were evaluated by the isovolumetric saturation method. The uptake of CO2 by the DES synthesized from betaine, 1,2-propanediol and 1,8-diazabicyclo(5.4.0)undec-7-ene reached a maximum of 1.5071 mol·kg−1 at 303.15 K and a pressure of 0.187 MPa. The simultaneous chemical and physical adsorption of CO2 by the ternary DESs was verified by FTIR spectroscopy, and the absorption mechanism was also proposed. The reaction equilibrium thermodynamic model (RETM) was improved to obtain the “Active DES” model, which was correlated with the experimentally determined CO2 solubility. The reaction equilibrium constants and Henry's law constants were obtained for each ternary system. The ternary superbase/betaine DESs proposed in this paper are green, economical and high-performance absorbers for capturing CO2.

Silver Recovery from E-Waste Printed Circuit Board Using Binary and Ternary Deep Eutectic Solvents

Printed Circuit Boards (PCBs) are essential components of electronic devices containing valuable silver metal. Using sustainable methods, silver recovery from electronic trash, like PCBs, demonstrates excellent promise. This research’s objective is to determine the optimum leaching time and solid-to-liquid (S/L) ratio for extracting silver from PCB using deep eutectic solvent (DES) composed of choline chloride and glycerol (glyceline DES). The binary DES’s leaching performance was then compared to choline chloride, glycerol, and citric acid ternary systems. Fourier Transform Infrared Spectroscopy (FTIR) was carried out to analyze the bond interactions. X-ray fluorescence spectrometry (XRF) was employed to determine the PCB’s metal concentration prior to and after the leaching process. Ternary DES was viscous, colorless, stable for 60 days, and less acidic than binary DES, with a 1.21 g/mL density. FTIR peak broadening and shifting indicated the formation of a new hydrogen bond and proved a successful synthesis of ternary DES. XRF result showed that PCB’s initial silver metal content was 2.32%. The optimal silver leaching from PCB using glyceline DES was achieved after 16 hours, with a 1/20 solid-to-liquid ratio. Ternary DES demonstrated a silver leaching efficiency of 93.65%, surpassing 86.77% of glyceline. Ternary DES synthesized in this study has the potential to serve as an efficient and environmentally friendly solvent for extracting silver from PCB, providing a sustainable approach to managing electronic waste.

Efficient and selective absorption of NH3 by supramolecular OHP[5]-based ternary deep eutectic solvents

Developing an efficient absorbent for selective ammonia capture is of significant importance in the recovery and utilization of ammonia resources. Herein, a series of supramolecular-based ternary deep eutectic solvents (DESs) was designed and prepared using per-hydroxy pillar[5]arene (OHP[5]) and ethylamine hydrochloride as the key components. It is found that the supramolecular-based ternary DES EaCl-Gly (1:2)-6% OHP[5] could be employed as an efficient absorbent for reversible absorption of NH3. The NH3 uptake capacity reached 2.39 mmol/g and 10.84 mmol/g at 298.2 K under the pressure of 10 kPa and 100 kPa, respectively. Meanwhile, a higher NH3/CO2 selectivity (84) was obtained at 298.2 K and 100 kPa owing to the low solubility of CO2 in EaCl-Gly (1:2)-6% OHP[5]. The results of 1H NMR and FTIR spectra further clarified the absorption mechanism of NH3 by EaCl-Gly (1:2)-6% OHP[5]. Accordingly, the chemical absorption and physical dissolution capacity of NH3 in EaCl-Gly (1:2)-6% OHP[5] were calculated on the basis of isotherm data and thermodynamic equations. This study offers a promising application of pillar[5]arene to form supramolecular-based DESs for efficient NH3 absorption.

Physicochemical and thermodynamic properties of binary amine-based deep eutectic solvents for carbon capture

Deep eutectic solvents (DESs) have attracted great interest as a new green alternative to ionic liquids. In order to investigate the potential of using DESs to replace traditional organic solvents in carbon capture processes, it is necessary to understand in detail the physicochemical and thermodynamic properties of DESs before and after CO2 absorption. In this paper, choline chloride was used as the hydrogen bond acceptor and ethanolamine as the hydrogen bond donor to prepare the original DES. Afterward, 5 % mass fraction of morpholine/sarcosine is then added to make two kinds of ternary secondary amine functionalized DESs. Six quaternary DESs were finally prepared by mixing 20 % solvent (water/glycerol/ethylene glycol) with the ternary DESs. Subsequently, the physicochemical properties of DESs, such as melting point, density, viscosity and surface tension, were experimentally determined over the temperature range of 303.15–353.15 K. The properties of ternary and quaternary DESs before and after CO2 absorption were especially predicted and analyzed using different models. It was found that the Vogel-Fulcher-Tamman model was more suitable for forecasting viscosity, and the Pelofsky equation was better for prediction of the relationship between surface tension and viscosity. Based on the experimental data and the solvent critical values predicted by the state equation, the thermodynamic properties of ternary and quaternary DESs before and after CO2 absorption, such as molar volume, isobaric expansion coefficient, lattice energy, activation energy, viscous flow entropy and enthalpy, were derived and analyzed.

Polysaccharides extraction from Ganoderma lucidum using a ternary deep eutectic solvents of choline chloride/guaiacol/lactic acid

In this study, a purposefully formulated ternary deep eutectic solvents (DESs), consisting of choline chloride, guaiacol, and lactic acid in a molar ratio of 1:1:1, was synthesized for the extraction of polysaccharides from Ganoderma lucidum. The physicochemical properties of the synthesized DESs, including viscosity, density, pH, and hydrogen bonds, were comprehensively examined. Verification of the formation of the ternary DESs was accomplished through Fourier transform infrared and Nuclear magnetic resonance spectroscopies. Subsequently, response surface methodology was applied to optimize crucial parameters for polysaccharide extraction using DESs, resulting in a maximal extraction yield of 94.72 mg/g under the optimized conditions. Cyclic experiments demonstrated the commendable cyclic stability of the DESs, with a recovery rate exceeding 88 %. Furthermore, experiments on monosaccharide composition, molecular weight, and antioxidant activity of the isolated polysaccharides were conducted. Density functional theory was employed to gain insights into the molecular mechanism of polysaccharide extraction by DESs. The findings revealed a triple hydrogen bond interaction and a high binding energy (65.29 kcal/mol) between the DESs and glucose, highlighting their significant contribution to the high extraction effectiveness. This molecular-level understanding underscores the inherent superiority of DESs in the polysaccharide extraction processes, providing valuable insights for future applications in this field.

Ternary deep eutectic solvents for efficient denitrogenation of a model oil: thermodynamics, extraction efficiency, and recycling performance

Ternary deep eutectic solvents for efficient denitrogenation of a model oil: thermodynamics, extraction efficiency, and recycling performance

Recyclable water-modified deep eutectic solvents for removal of multiple heavy metals from soil

Removing heavy metals from soil has always been a challenge in terms of safety and effectiveness. Deep eutectic solvents (DESs) are recognized as environmentally friendly reagents with great potential in the removal of heavy metals from soil. In this study, water was introduced as a third component to form new ternary deep eutectic water solvents (DEWSs) to improve their performance. The removal capacity, applicable conditions and mechanisms of sixteen DEWSs for heavy metals were systematically investigated. Experimental results showed that the presence of water significantly enhanced the removal efficiency of three DESs (Choline chloride plus Urea, DEU; Choline chloride plus l-lactic acid, DELA; and Choline chloride plus Ethylene glycol, DEEG) for heavy metals. However, as the molar ratio of water increased, the eutectic systems in the DEWSs weakened and eventually disappeared. Under optimum conditions, DEWLA7 (DELA : H2O = 2 : 8) showed the highest removal rate for cadmium, lead, copper and zinc, which were 43.42%, 94.73%, 90.72% and 96.44%, respectively. Hydrogen bonding, adsorption of oxygen functional groups, exchangeable hydrogen substitution, changes in viscosity properties and co-precipitation all contributed to the removal of heavy metals by DEWLA7. Notably, DEWLA7 had no significant effect on the content of major minerals and nutrients in the soil. Furthermore, DEWLA7 proved to be reusable for soil washing, and still retains a high removal rate of 37.32%–83.66% after multi-stage filtration treatment. Therefore, DEWLA7 was an unexplored and excellent soil washing agent with great potential in economic and social benefits.

Ternary deep eutectic solvents for esterification of 2-methylpropenoic acid with alcohols.

In this paper, a set of novel ternary deep eutectic solvents (T-DESs) is synthesized and applied in the esterification of 2-methylpropenoic acid with alcohols. T-DESs have multiple functions, serving as a catalyst, polymerization inhibitor, and solvent, and demonstrate excellent catalytic esterification reaction activity (up to 96% yield). The optimal T-DESs 1 can be recycled 14 times without any decrease in its catalytic activity, thus solving the problems of methacrylate product separation with a polymerization inhibitor, catalyst recovery, and organic solvent pollution.