Deep eutectic solvents for separation and purification applications in critical metal metallurgy:Recent advances and perspectives

Solvent extraction,a separation and purification technology,is crucial in critical metal metallurgy.Organic solvents commonly used in solvent extraction exhibit disadvantages,such as high volatility,high toxicity,and flammability,causing a spectrum of hazards to human health and environmental safety.Neoteric solvents have been recognized as potential alternatives to these harmful organic solvents.In the past two decades,several neoteric solvents have been proposed,including ionic liquids(ILs)and deep eutectic solvents(DESs).DESs have gradually become the focus of green solvents owing to several advantages,namely,low toxicity,degradability,and low cost.In this critical review,their classification,formation mechanisms,preparation methods,characterization technologies,and special physicochemical properties based on the most recent advancements in research have been systematically described.Subsequently,the major separation and purification applications of DESs in critical metal metallurgy were comprehensively summarized.Finally,future opportunities and challenges of DESs were explored in the current research area.In conclusion,this review provides valuable insights for improving our overall understanding of DESs,and it holds important potential for expanding separation and purification applications in critical metal metallurgy.

Efficient and reversible separation of NH_(3) by deep eutectic solvents with multiple active sites and low viscosities

The efficient separation and collection of ammonia(NH_(3))during NH_(3) synthesis process is essential to improve the economic efficiency and protect the environment.In this work,ethanolammonium hydrochloride(EtOHACl)and phenol(PhOH)were used to prepare a novel class of deep eutectic solvents(DESs)with multiple active sites and low viscosities.The NH_(3) separation performance of EtOHACl+PhOH DESs was analyzed completely.It is figured out that the NH_(3) absorption rates in EtOHACl+PhOH DESs are very fast.The NH_(3) absorption capacities are very high and reach up to 5.52 and 10.74 mol·kg1 at 11.2 and 100.4 kPa under 298.2 K,respectively.In addition,the EtOHACl+PhOH DESs present highly selective absorption of NH_(3) over N_(2) and H_(2) and good regenerative properties after seven cycles of absorption/desorption.The intrinsic separation mechanism of NH_(3) by EtOHACl+PhOH DESs was further revealed by spectroscopic analysis and quantum chemistry calculations.

Insight into the experiment and extraction mechanism for separating carbazole from anthracene oil with quaternary ammonium-based deep eutectic solvents

Carbazole is an irreplaceable basic organic chemical raw material and intermediate in industry.The separation of carbazole from anthracene oil by environmental benign solvents is important but still a challenge in chemical engineering.Deep eutectic solvents (DESs) as a sustainable green separation solvent have been proposed for the separation of carbazole from model anthracene oil.In this research,three quaternary ammonium-based DESs were prepared using ethylene glycol (EG) as hydrogen bond donor and tetrabutylammonium chloride (TBAC),tetrabutylammonium bromide or choline chloride as hydrogen bond acceptors.To explore their extraction performance of carbazole,the conductor-like screening model for real solvents (COSMO-RS) model was used to predict the activity coefficient at infinite dilution (γ^(∞)) of carbazole in DESs,and the result indicated TBAC:EG (1:2) had the stronger extraction ability for carbazole due to the higher capacity at infinite dilution (C^(∞)) value.Then,the separation performance of these three DESs was evaluated by experiments,and the experimental results were in good agreement with the COSMO-RS prediction results.The TBAC:EG (1:2) was determined as the most promising solvent.Additionally,the extraction conditions of TBAC:EG (1:2) were optimized,and the extraction efficiency,distribution coefficient and selectivity of carbazole could reach up to 85.74%,30.18 and 66.10%,respectively.Moreover,the TBAC:EG (1:2) could be recycled by using environmentally friendly water as antisolvent.In addition,the separation performance of TBAC:EG (1:2) was also evaluated by real crude anthracene,the carbazole was obtained with purity and yield of 85.32%,60.27%,respectively.Lastly,the extraction mechanism was elucidated byσ-profiles and interaction energy analysis.Theoretical calculation results showed that the main driving force for the extraction process was the hydrogen bonding ((N–H...Cl) and van der Waals interactions (C–H...O and C–H...π),which corresponding to the blue and green isosurfaces in IGMH analysis.This work presented a novel method for separating carbazole from crude anthracene oil,and will provide an important reference for the separation of other high value-added products from coal tar.

Machine-Learning-Assisted Design of Deep Eutectic Solvents Based on Uncovered Hydrogen Bond Patterns

Non-ionic deep eutectic solvents(DESs)are non-ionic designer solvents with various applications in catalysis,extraction,carbon capture,and pharmaceuticals.However,discovering new DES candidates is challenging due to a lack of efficient tools that accurately predict DES formation.The search for DES relies heavily on intuition or trial-and-error processes,leading to low success rates or missed opportunities.Recognizing that hydrogen bonds(HBs)play a central role in DES formation,we aim to identify HB features that distinguish DES from non-DES systems and use them to develop machine learning(ML)models to discover new DES systems.We first analyze the HB properties of 38 known DES and 111 known non-DES systems using their molecular dynamics(MD)simulation trajectories.The analysis reveals that DES systems have two unique features compared to non-DES systems:The DESs have①more imbalance between the numbers of the two intra-component HBs and②more and stronger inter-component HBs.Based on these results,we develop 30 ML models using ten algorithms and three types of HB-based descriptors.The model performance is first benchmarked using the average and minimal receiver operating characteristic(ROC)-area under the curve(AUC)values.We also analyze the importance of individual features in the models,and the results are consistent with the simulation-based statistical analysis.Finally,we validate the models using the experimental data of 34 systems.The extra trees forest model outperforms the other models in the validation,with an ROC-AUC of 0.88.Our work illustrates the importance of HBs in DES formation and shows the potential of ML in discovering new DESs.

Sodium Nitrate/Formamide Deep Eutectic Solvent as Flame-Retardant and Anticorrosive Electrolyte Enabling 2.6 V Safe Supercapacitors with Long Cyclic Stability

Safe operation of electrochemical capacitors(supercapacitors)is hindered by the flammability of commercial organic electrolytes.Non-flammable Water-in-Salt(WIS)electrolytes are promising alternatives;however,they are plagued by the limited operation voltage window(typically≤2.3 V)and inherent corrosion of current collectors.Herein,a novel deep eutectic solvent(DES)-based electrolyte which uses formamide(FMD)as hydrogen-bond donor and sodium nitrate(NaNO_(3))as hydrogen-bond acceptor is demonstrated.The electrolyte exhibits the wide electrochemical stability window(3.14 V),high electrical conductivity(14.01 mScm^(-1)),good flame-retardance,anticorrosive property,and ultralow cost(7%of the commercial electrolyte and 2%of WIS).Raman spectroscopy and Density Functional Theory calculations reveal that the hydrogen bonds between the FMD molecules and NO_(3)^(-)ions are primarily responsible for the superior stability and conductivity.The developed NaNO_(3)/FMD-based coin cell supercapacitor is among the best-performing state-of-art DES and WIS devices,evidenced by the high voltage window(2.6 V),outstanding energy and power densities(22.77 Wh kg^(-1)at 630 W kg^(-1)and 17.37 kW kg^(-1)at 12.55 Wh kg^(-1)),ultralong cyclic stability(86%after 30000 cycles),and negligible current collector corrosion.The NaNO_(3)/FMD industry adoption potential is demonstrated by fabricating 100 F pouch cell supercapacitors using commercial aluminum current collectors.

Study on the green extraction of corncob xylan by deep eutectic solvent

Corn as one of the world's major food crops,its by-product corn cob is also rich in resources.However,the unreasonable utilization of corn cob often causes the environmental pollution,waste of resources and other problems.As one of the most abundant polymers in nature,xylan is widely used in food,medicine,materials and other fields.Corn cob is rich in xylan,which is an ideal raw material for extracting xylan.However,the intractable lignin is covalently linked to xylan,which increases the difficulty of xylan extraction.It has been reported that the deep eutectic solvent(DES)could preferentially dissolve lignin in biomass,thereby dissolving the xylan.Then,the xylan in the extract was separated by ethanol precipitation method.The xylan precipitate was obtained after centrifugation,while the supernatant was retained.The components of the supernatant after ethanol precipitation were separated by the rotary evaporator.The ethanol,water and DES were collected for the subsequent extraction of corn cob xylan.In this study,a novel way was provided for the green production of corn cob xylan.The DES was used to extract xylan from corn cob which was used as the raw material.The effects of solid-liquid ratio,reaction time,reaction temperature and water content of DES on the extraction rate of corn cob xylan were investigated by the single factor test.Furthermore,the orthogonal test was designed to optimize the xylan extraction process.The structure of corn cob xylan was analyzed and verified.The results showed that the optimum extraction conditions of corn cob xylan were as follows:the ratio of corn cob to DES was 1:15(g:mL),the extraction time was 3 h,the extraction temperature was 60℃,and the water content of DES was 70%.Under these conditions,the extraction rate of xylan was 16.46%.The extracted corn cob xylan was distinctive triple helix of polysaccharide,which was similar to the structure of commercially available xylan.Xylan was effectively and workably extracted from corn cob by the DES method.This study provided a new approach for high value conversion of corn cob and the clean production of xylan.

Oxidative Desulfurization of Fuel Oil with H_(3)PO_(4)-based Deep Eutectic Solvents

A series of Lewis-acid deep eutectic solvents (DESs) were synthesized by stirring phosphoric acid and zincchloride as raw materials at 80℃ to form H_(3)PO_(4)/nZnCl_(2) (n = 0.1, 0.25, 0.5, 0.75, 1). The DESs were characterized byFourier transform infrared spectrophotometry (FT-IR), thermogravimetry/differential thermogravimetry (TG/DTG), andelectron spray ionization mass spectrometry (ESI-MS). The DESs were used as both extractants and catalysts to removedibenzothiophene from fuels via oxidative desulfurization (ODS). Experiments were performed to investigated the influenceof factors such as composition of DES, temperature, oxidant dosage (molar ratio of O:S), DES dosage (volume ratio ofDES:oil), and number of cycles on desulfurization rate. The results indicated that the removal rate of dibenzothiophene (DBT)was affected by the Lewis acidic DESs, with that of H_(3)PO_(4)/0.25∙ZnCl_(2) reaching 96.4% under optimal conditions (Voil=5 mL,VDES=1 mL, an oxidant dosage of 6, T=50 ℃). After six cycles, the desulfurization rate of H_(3)PO_(4)/0.25∙ZnCl_(2) remained above94.1%. The apparent activation energy of dibenzothiophene (DBT) removal reaction was determined by a pseudo-first orderkinetic equation according to the Arrhenius equation to be 32.34 kJ/mol, as estimated. A reaction mechanism is proposedbased on the experimental data and characterization results.

Research Progress of Deep Eutectic Solvents in Extraction of Plant Flavonoids

As a new type of green solvents,deep eutectic solvents(DESs)have the advantages of strong extraction ability,designability,simple preparation,low price,recoverability and biodegradation,and show great application potential in the field of plant flavonoid extraction.In this paper,the definition,classification and preparation methods of DESs were introduced.The effects of DES composition,molar ratio of DES components,water content of DES systems,liquid-material ratio,extraction temperature,extraction time and extraction auxiliary techniques on the extraction yield of plant flavonoids were expounded.The recycling methods of DESs were summarized.Existing problems of DESs in the field of plant flavonoids extraction were pointed out,and further research direction and trend were analyzed and prospected.

Investigation of oligomeric proanthocyanidins extracted from Rhodiolae Crenulatae Radix et Rhizomes using deep eutectic solvents and identified via data-dependent acquisition mass-spectroscopy

In this study,34 deep eutectic solvents(DESs)were successfully prepared for the extraction of proanthocyanidin from Rhodiolae Crenulatae Radix et Rhizomes.The extraction process was optimized using single factor exploration and Box-Behnken design-response surface analysis.The extraction rate was significantly improved when the molar ratio of choline chloride to 1,3-propanediol was 1:3.5 and the water content was 30%(V/V)in DESs.AB-8 macroporous resin and ethyl acetate were used for separation and refining,and the oligomer-rich proanthocyanidin components were eventually obtained.The ultraviolet(UV)and infrared(IR)spectra showed that the proanthocyanidins were mainly composed of catechin and epicatechin.To further clarify the chemical composition of proanthocyanidin,an ion scan list containing 156 proanthocyanidins precursors was obtained by constructing a proanthocyanidins structural library and mass defect filtering(MDF)algorithm,combined with the full mass spectrometry(MS)/dd-MS2 scan mode that turns on the“if idle pick others”function.By using ultra-high performance liquid chromatography and high-resolution MS(UHPLC/HRMS),the analysis used both targeted and nontargeted methods to detect proanthocyanidins.Finally,50 oligomeric proanthocyanidin(OPC)compounds were identified,including 7 monomers,22 dimers,20 trimers,and 1 tetramer,most of which were procyanidins of proanthocyanidins(84%),and a small amount of prodelphinidin(14%)and other types of proanthocyanidins(2%),which enabled the systematic characterization of proanthocyanidin components from Rhodiolae Crenulatae Radix et Rhizomes.Meanwhile,the comparison with the grape seeds OPCs standard(United States Pharmacopeia)revealed that the proanthocyanidins in Rhodiolae Crenulatae Radix et Rhizomes were more abundant,suggesting that the proanthocyanidins in Rhodiolae Crenulatae Radix et Rhizomes has promising applications.

Nucleation and growth of eutectic cell in hypoeutectic Al-Si alloy

The nucleation and growth of eutectic cell in hypoeutectic Al-Si alloy was investigated using optical microscopy and scanning electron microscopy equipped with electron backscattering diffraction（EBSD）.By revealing the eutectic cells and analyzing the crystallographic orientation,it was found that both the eutectic Si and Al phases in an eutectic cell were not single crystal,representing an eutectic cell consisting of small ＇grains＇.It is also suggested that the eutectic nucleation mode can not be determined based on the crystallographic orientation between eutectic Al phases and the neighboring primary dendrite Al phases.However,the evolution of primary dendrite Al phases affects remarkably the following nucleation and growth of eutectic cell.The coarse flake-fine fibrous transition of eutectic Si morphology involved in impurity elements modification may be independent of eutectic nucleation.

Ultrasonic assisted natural deep eutectic solvents as a green and efficient approach for extraction of hydroxytyrosol from olive leaves

In this study,an ultrasonic assisted natural deep eutectic solvent(DES)was used to extract hydroxytyrosol(HT)from olive leaves.The optimal extraction conditions of the MaPa-4 concentration,extraction time and solid-liquid ratio were obtained by single factor experiments.The formation mechanism of MaPa and its interaction with HT were analyzed by FTIR,^(1)H-NMR and density functional theory(DFT)calculation.Then,MaPa-4 and water extracts obtained under the optimal extraction conditions were selected for a series of efficacy tests.MaPa-4 extract demonstrated low cytotoxicity,good biocompatibility,and excellent antiinflammatory and bacteriostatic properties.Overall,MaPa-4,as an environmentally friendly and efficient solvent,was combined with ultrasound treatment to develop an efficient,green and feasible method to extract HT from olive leaves.

Stoichiometry and Stability Constant Values for Copper (II) Chelates with Ethylene Diamine in Deep Eutectic Solvents (DES) (Ethaline) Solutions

In this study we used the deep eutectic solvents (ionic liquids) to investigate the reaction between copper (II) with ethylene diamine (en). Two of the existing methods for analyzing spectrophotometric measurements have been applied for establishing, the stoichiometry and whenever possible, the stability constants of the chelates formed. The method of continuous variations was necessary to determine first whether, the metal ion and the ligand ethylene diamine form one or more than one chelate, when more than one chelate formed, the results obtained depend on the wavelength and for meaningful conclusions the wavelengths were carefully selected. The empirical formulae of the chelates were further substantiated by the molar ratio method. The effect of time and temperature on the formation and stability of these chelates in solution is also studied. The stability constants, K1 and K2 for the copper (II) chelates were calculated, though reliable, and are comparable to literature values.

High temperature oxidation behavior of directionally solidified NiAl-31Cr-2.9Mo-0.1Hf-0.05Ho eutectic alloy

The isothermal oxidation behavior of NiAl-31Cr-2.9Mo-0.1Hf-0.05Ho directional eutectic alloy was investigated with the help of scanning electron microscopy and X-ray diffraction.The results revealed that a continuous Al2O3 scale was formed and owned excellent oxidation resistance in the temperature range of 900-1100°C.When the temperature was up to 1150°C,the continuous Al2O3 oxide film ruptured.Trace rare earth element Ho distributed uniformly in the alloy and relatively high level of Al in Cr（Mo）phase are beneficial to the formation of continuous and compact Al2O3 scale.During the oxidation,a phase transformation fromθ-Al2O3 toα-Al2O3 existed on the surface of oxidation film.It resulted in the abnormal oxidation mass gain happening when the alloy was oxidized at 1000°C or 1050°C.

Effect of Sr modification on microstructure and thermal conductivity of hypoeutectic Al−Si alloys

Trace amount of Sr(0.05 wt.%)was added into the hypoeutectic Al−Si(3−12 wt.%Si)alloys to modify their microstructure and improve thermal conductivity.The results showed that the thermal conductivity of hypoeutectic Al−Si alloys was improved by Sr modification,and the increment and increasing rate of the thermal conductivity gradually increased with Si content increasing.The improvement of thermal conductivity was primarily related to the morphology variation of eutectic Si phases.In Sr-modified Al−Si alloys,the morphology of eutectic Si phases was a mixed morphology of fiber structure and fine flaky structure,and the proportion of the fine flaky eutectic Si phases gradually decreased with Si content increasing.Under the Si content reaching 9 wt.%,the proportion of fine flaky eutectic Si phases was nearly negligible in Sr-modified alloys.Correspondingly,the increment and increasing rate of thermal conductivity of Sr-modified alloys reached the maximum and tended to be stable.

Eutectic nucleation in Al-25wt.% Si alloy through DSC

Eutectic nucleation in hypereutectic Al-25wt.%Si alloy with the addition of P was studied by calculating the activation energy and nucleation work. The results indicate that P refinement, which can decrease the activation energy as well as nucleation work of eutectic solidification, can increase the eutectic nucleation frequency of Al-25wt.%Si alloy, so the addition of P can refme the eutectic structures of hypereutectic Al-Si alloys. According to the calculations, there is a certain relationship between the precipitation of primary silicon and eutectic solidification, and the eutectic nucleation mode is independent of morphology transition.

Relationship between amounts of low-melting-point eutectics and hot tearing susceptibility of ternary Al−Cu−Mg alloys during solidification

A systematical study on the relationship between the amounts of different eutectic phases especially the low-melting-point(LMP)eutectics and the hot tearing susceptibility of ternary Al−Cu−Mg alloys during solidification was performed.By controlling the concentrations of major alloying elements(Cu,Mg),the amounts of LMP eutectics at the final stages of solidification were varied and the corresponding hot tearing susceptibility(HTS)was determined.The results showed that the Al−4.6Cu−0.4Mg(wt.%)alloy,which contained the smallest fraction of LMP eutectics among the investigated alloys,was observed to be the most susceptible to hot tearing.With the amount of total residual liquid being approximately the same in the alloys,the hot tearing resistance is considered to be closely related to the amounts of LMP eutectics.Specifically,the higher the amount of LMP eutectics was,the lower the HTS of the alloy was.Further,the potential mechanism of low HTS for alloys with high amounts of LMP eutectics among ternary Al−Cu−Mg alloys was discussed in terms of feeding ability and permeability as well as total viscosity evolution during solidification.

HR-TEM and FIB-SEM characterization of formation of eutectic-like structure from amorphous GdAlO_3-Al_2O_3 system

The crystallization process of the eutectic composition of GdAlO_3-Al_2O_3 from the amorphous phase prepared by rapid-quenching of melt that leads to the formation of a cantaloupe skin-like microstructure was investigated using focused ion-beam scanning electron microscopy (FIB-SEM) and high-resolution transmission electron microscopy (HR-TEM).The amorphous films were heat-treated at temperatures between 1000 °C and 1500 °C for up to 30min to form the eutectic phases of GdAlO_3 and Al_2O_3.The GdAlO_3 and Al_2O_3 crystal phases that formed from the amorphous phase were identified by FIB-SEM and HR-TEM.Both components began to crystallize and grow from the amorphous phase separately at different temperatures.The formation process of these crystal phases was different from that of the ordinary eutectic microstructure solidified from the GdAlO_3-Al_2O_3 system.Therefore,the observed structure is termed "eutectic-like" for distinction.The microstructures formed from the amorphous phases at sufficiently high temperatures consisted of ultra-fine microstructures of individually crystallized components and were similar to ordinary eutectic microstructures.By heat-treating the amorphous films at 1500 °C for either 2 min,8min or 30min,the ultra-fine components of GdAlO_3 and Al_2O_3 were found to crystallize following a eutectic-like stage after 8min of heat treatment.

Effect of Cerium on Morphology of Phosphide Eutectic

The phosphide eutectic formation process in high purity Fe-4. 6% C alloy, in which 0.02%-1.0% P was added, was studied with DTA, SEM and EDS, and the effect of cerium on the morphology of phosphide eutectic in the ternary Fe-C-P alloy was also investigated. The results show that the ternary phosphide eutectic with the addition of 0.04% P is formed at low cooling rate. After cerium is added, the morphology of phosphide eutectic is changed from non-continuous or continuous distribution net to round or nodular form locating along the eutectic cell boundaries.

Microstructure optimization of directionally solidified hypereutectic Nb-Si alloy

Nb-16Si-24Ti-10Cr-2A1-2Hf alloy was directionally solidified with withdrawal rates of 1.2, 6, 18, 36 and 50 mrn/min and then heat treated at 1400, 1450 and 1500℃with withdrawal rate of 50 mm/min for 10 h. The effects of withdrawal rate and heat treatment temperature on the microstructure were studied. The microstructure of directionally solidified alloy was composed of the primary NbsSi3, Nbss/NbsSi3 eutectic cells and Cr2Nb, which distribute paralleled to the growth direction. The microstructure becomes more refined with the increasing withdrawal rate, accompany with the evolution of eutectic cells morphology. After heat treatment, Nbss phase connects and forms a continuous matrix, and the Cr2Nb phase becomes smaller and distributes more dispersedly. After heat treatment at 1450 ℃ for 10 h, the alloy achieves balance between the optimization of microstructure and alleviation of solute segregation.

Hydrogen diffusion coefficient in liquid metals evaluated by solid-gas eutectic unidirectional solidification

Based on the solid-gas eutectic unidirectional solidification technique and the principle of unidirectional solidification of single-phase alloy, a new method for evaluating the diffusion coefficient of hydrogen in liquid metals was proposed. Taking Cu-H2 system for example, the influences of argon partial pressure and superheat degree of melt on the diffusion coefficient of hydrogen in liquid metal were studied and the predicted values were similar to each other. The obtained temperature-dependent equation for diffusion coefficient of hydrogen in liquid copper is comparable with experimental data in literature, which validates the effectiveness of this method. The temperature-dependent equations for diffusion coefficient of hydrogen in liquid Mg, Si and Cu-34.6%Mn alloy were also evaluated by this method, along with the values at the melting point of each metal and alloy.