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)...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.展开更多
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 che...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.展开更多
A series of Lewis-acid deep eutectic solvents (DESs) were synthesized by stirring phosphoric acid and zincchloride as raw materials at 80 °C to form H_(3)PO_(4)/nZnCl_(2) (n = 0.1, 0.25, 0.5, 0.75, 1). The DESs w...A series of Lewis-acid deep eutectic solvents (DESs) were synthesized by stirring phosphoric acid and zincchloride as raw materials at 80 °C 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.展开更多
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 ...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.展开更多
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 pote...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.展开更多
As the demand for sustainable energy sources continues to rise,the need for efficient and reliable energy storage systems becomes crucial.In order to effectively store and distribute renewable energy,new and innovativ...As the demand for sustainable energy sources continues to rise,the need for efficient and reliable energy storage systems becomes crucial.In order to effectively store and distribute renewable energy,new and innovative solutions must be explored.This review examines the deep eutectic solvents(DESs)as a green,safe,and affordable solution for the electrochemical energy storage and conversion field,offering tremendous opportunities and a promising future.DESs are a class of environment-friendly solvents known for their low toxicity and unique properties,such as their good conductivity,high thermal stability,and nonflammability.This review explores the fundamentals,preparations,and various interactions that often predominate in the formation of DESs,the properties of DESs,and how DESs are better than traditional solvents involving cost-ineffective and unsafe organic electrolytes and ionic liquids as well as inefficient aqueous systems due to low energy density for electrochemical energy storage applications.Then,a particular focus is placed on the various electrochemical applications of DESs,including their role in the electrolytes in batteries/supercapacitors,electropolishing and electrodeposition of metals,synthesis of electrode materials,recycling of electrodes,and their potential for use in CO_(2)capture.The review concludes by exploring the challenges,research gaps,and future potential of DESs in electrochemical applications,providing a comprehensive overview,and highlighting key considerations for their design and use.展开更多
Levulinic acid(LA)is one of the top-12 most promising biomass-based platform chemicals,which has a wide range of applications in a variety of fields.However,separation and purification of LA from aqueous solution or a...Levulinic acid(LA)is one of the top-12 most promising biomass-based platform chemicals,which has a wide range of applications in a variety of fields.However,separation and purification of LA from aqueous solution or actual hydrolysate continues to be a challenge.Among various downstream separation technologies,liquid-liquid extraction is a low-cost,effective,and simple process to separate LA.The key breakthrough lies in the development of extractants with high extraction efficiency,good hydrophobicity,and low cost.In this work,three hydrophobic deep eutectic solvents(DESs)based on tri-n-octylamine(TOA)as hydrogen bond acceptor(HBA)and alcohols(butanol,2-octanol,and menthol)as hydrogen bond donors(HBDs)were developed to extract LA from aqueous solution.The molar ratios of HBD and HBA,extraction temperature,contact time,solution pH,and initial LA concentration,DES/water volume ratios were systematically investigated.Compared with 2-octanol-TOA and menthol-TOA DES,the butanol-TOA DES exhibited the superior extraction performance for LA,with a maximum extraction efficiency of 95.79±1.4%.Moreover,the solution pH had a great impact on the LA extraction efficiency of butanol-TOA(molar ratio=3:1).It is worth noting that the extraction equilibrium time was less than 0.5 h.More importantly,the butanol-TOA(3:1)DES possesses good extraction abilities for low,medium,and high concentrations of LA.展开更多
Sinomenine is the main bio-active ingredient of Sinomenii Caulis and usually produced by solventextraction techniques. However, the extraction of sinomenine suffers from the lack of highly efficient and environmentall...Sinomenine is the main bio-active ingredient of Sinomenii Caulis and usually produced by solventextraction techniques. However, the extraction of sinomenine suffers from the lack of highly efficient and environmentally-benign solvents. In this work, deep eutectic solvents(DESs) based on fragrances were synthesized, hydrogen-bond donors(HBDs) and hydrogen-bond acceptors(HBAs) components of DESs were identified and their extraction ability for sinomenine was evaluated and the extraction conditions were optimized by single-factor and orthogonal design experiments. It was found that the hydrogen-bonding interaction between sinomenine and DESs was the main extraction driving force and there was no explicit relationship between the extraction ability and the hydrophobicity of the DESs. The DESs could be recycled and sinomenine could be recovered quantitatively via backextraction. High-purity sinomenine((95.0 ± 2.3)%) could be produced. These findings suggest that DESs are highly-effective solvents for the isolation of sinomenine and exhibit great potential for the extraction of other bio-active compounds.展开更多
Important efforts have been made over the past years to improve the drug acts,which leads to the discovery of novel drug preparations and delivery systems.The optimal design of such processes requires a molecular-leve...Important efforts have been made over the past years to improve the drug acts,which leads to the discovery of novel drug preparations and delivery systems.The optimal design of such processes requires a molecular-level understanding of the interactions between drug molecules and biological membranes.The thermodynamic investigation provides deep and complete knowledge of interactions and the choice of appropriate and suitable production compounds in pharmaceutical fields.Particularly,the analysis of drugs+co-solvents in aqueous media is the central issue in many types of research because they exert their impact by interacting with biological membranes.This work is aimed to measure the density and speed of sound for the thiamine hydrochloride in water+deep eutectic solvents(DESs)mixtures(choline chloride/urea,choline chloride/ethylene glycol and choline chloride/glycerol)at temperature range(293.15-308.15)K.By correlation of the evaluated parameters in some standard relations,the partial molar parameters i.e.apparent molar volumes,Vφ,m,and apparent molar isentropic compression,κ_(s,φ,m),are calculated.In addition,apparent molar isobaric expansion,E^(0)_(φ,m),and Hepler’s constant are computed from the density and speed of sound data.For fitting the experimental Vφ,m andκ_(s,φ,m)the Redlich-Meyer equation was employed that the important quantities;standard partial molar volume,V^(0)_(m),and partial molar isentropic compression,κφ,m0,were obtained.The thermodynamic analysis of the studied system also plays a crucial role in the pharmaceutical industry.展开更多
The development of green solvents for enhancing aqueous solubility of drug curcumin remains a challenge. This study explores the enhancing effect of deep eutectic solvents(DESs) on the aqueous solubility of curcumin(C...The development of green solvents for enhancing aqueous solubility of drug curcumin remains a challenge. This study explores the enhancing effect of deep eutectic solvents(DESs) on the aqueous solubility of curcumin(CUR) via experiment and theoretical calculation. Choline chloride-based DESs with polyols 1,2-propanediol(1,2-PDO), 1,3-propanediol, ethylene glycol, and glycerol as hydrogen bond donors were prepared and used as co-solvents. The CUR aqueous solubility increased with increasing the DESs content at temperature of 303.15-318.15 K, especially in aqueous ChCl/1,2-PDO(mole ratio 1:4) solutions. The positive apparent molar volume values and reduced density gradient analysis confirmed the existence of strong interactions between CUR and solvent. The van der Waals interactions and hydrogen bonding coexisted in DESs monomer retained the stability of DESs structure after introducing CUR. Moreover,the lower interaction energy of DESs…CUR system than that of the counterpart DESs further proved the strong interaction between CUR and DESs. The lowest interaction energy of ChCl/1,2-PDO…CUR system indicated that this system was the most stable and ChCl/1,2-PDO was promising for CUR dissolution.This work provides efficient solvents for utilizing curcumin, contributing to a deep insight into the interactions between DES and CUR at the molecular level, and the role of DESs on enhancing drugs solubility.展开更多
Fracturing fluid property play a critical role in developing unconventional reservoirs.Deep eutectic solvents(DESs)show fascinating potential for property improvement of clean fracturing fluids(CFFs)due to their low-p...Fracturing fluid property play a critical role in developing unconventional reservoirs.Deep eutectic solvents(DESs)show fascinating potential for property improvement of clean fracturing fluids(CFFs)due to their low-price,low-toxicity,chemical stability and flexible designability.In this work,DESs were synthesized by mixing hydrogen bond acceptors(HBAs)and a given hydrogen bond donor(HBD)to explore their underlying influence on CFF properties based on the intermolecular interactions.The hydrogen-bonding,van der Waals and electrostatic interactions between DES components and surfactants improved the CFF properties by promoting the arrangement of surfactants at interface and enhancing the micelle network strength.The HBD enhanced the resistance of CFF for Ca^(2+) due to coordination-bonding interaction.The DESs composed of choline chloride(ChCl)and malonic acid show great enhancement for surface,rheology,temperature resistance,salt tolerance,drag reduction,and gel-breaking performance of CFFs.The DESs also improved the gel-breaking CFF-oil interactions,increasing the imbibition efficiencies to 44.2%in 74 h.Adjusting HBAs can effectively strengthen the intermolecular interactions(e.g.,HBA-surfactant and HBD-surfactant interactions)to improve CFF properties.The DESs developed in this study provide a novel strategy to intensify CFF properties.展开更多
Ni-Fe bimetallic electrodes are currently recognized as a kind of benchmark transition metal-based oxygen evolution reaction(OER)electrocatalysts.Facile synthesis of Ni-Fe bimetallic electrode materials with excellent...Ni-Fe bimetallic electrodes are currently recognized as a kind of benchmark transition metal-based oxygen evolution reaction(OER)electrocatalysts.Facile synthesis of Ni-Fe bimetallic electrode materials with excellent catalytic activity and satisfied stability by a simple and low-cost route is still a big challenge.Herein,well-defined Ni-Fe nanoparticles in-situ developed on a planar Fe substrate(Ni-Fe NPs/Fe)is fabricated via a facile one-step galvanic replacement reaction(GRR)carried out in an Ethaline-based deep eutectic solvent(DES).The prepared Ni-Fe NPs/Fe exhibits outstanding OER performance,which needs an overpotential of only 319 mV to drive a current density of 10 mA cm^(-2),with a small Tafel slope of 41.2 mV dec^(-1) in 1.0 mol L^(-1) KOH,high mass activity(up to 319.78 A g^(-1) at an overpotential of 300 mV)and robust durability for 200 h.Impressively,the Ni-Fe bimetallic oxygen-evolution electrode obtained from the Ethaline-based DES is catalytically more active and durable than that of its counterpart derived from the 4.2 mol L^(-1) NaCl aqueous solution.The reason for this is mainly related to the different morphology and surface state of the Ni-Fe catalysts obtained from these different solvent environments,particularly for the differences in phy-chemical properties,active species formed and deposition kinetics,offered by the Ethaline-based DES.展开更多
Deep eutectic solvents(DESs) are a new class of green solvents analogous to ionic liquids due to their biodegradable capacity and low cost. However, the direct extractive desulfurization of diesel oil by DESs cannot m...Deep eutectic solvents(DESs) are a new class of green solvents analogous to ionic liquids due to their biodegradable capacity and low cost. However, the direct extractive desulfurization of diesel oil by DESs cannot meet the government’s standard. In this work, amphiphilic polyoxometalates were synthesized and characterized by FT-IR and mass spectrometry.The oxidative desulfurization results showed that benzothiophene(BT) could be completely removed by employing a [(CH)P(CH)]PMoO, DES(ChCl/2 Ac) and HOsystem. It was also found that the organic cation of catalysts played a positive role in oxidative desulfurization. The reaction conditions, such as reaction temperature and time, the amount of catalyst and DES and HO/S(O/S) molar ratio, were optimized. Different sulfides were tested to determine the desulfurization selectivity of the optimal reaction system, and it was found that 97.2% of dibenzothiophene(DBT) could be removed followed by 80.7% of 4-MDBT and 76.0% of 4,6-DMDBT. After reaction, the IR spectra showed that the catalyst [(CH)P(CH)]PMoOwas stable during the reaction process and the oxidative product was dibenzothiophene sulfone(DBTO). Furthermore, the catalyst can be regenerated and recycled for four runs with little loss of activity.展开更多
This review divides the acidic deep eutectic solvents(ADES) into Br?nsted and Lewis DES according to their diversity of acidic character.The hydrogen bond donors and halide salts for formulating an ADES are classified...This review divides the acidic deep eutectic solvents(ADES) into Br?nsted and Lewis DES according to their diversity of acidic character.The hydrogen bond donors and halide salts for formulating an ADES are classified, the synthesis methods are described, and the physicochemical properties including freezing point, acidity, density, viscosity and conductivity are presented. Furthermore, the applications of Br?nsted acidic deep eutectic solvents(BADES) and Lewis acidic deep eutectic solvents(LADES) are overviewed, respectively, covering the fields in dissolution, extraction, organic reaction and metal electrodeposition. It is expected that the ADES has great potential to replace the pollutional mineral acid, expensive and unstable solid acid, and costly ionic liquid in many acid-employed chemical processes, thus meeting the demands of green chemistry.展开更多
The CO_(2)solubilities(including CO_(2)Henry’s constant)in physical-and chemical-based ILs/DESs and the COSMO-RS models describing these properties were comprehensively collected and summarized.The summarized results...The CO_(2)solubilities(including CO_(2)Henry’s constant)in physical-and chemical-based ILs/DESs and the COSMO-RS models describing these properties were comprehensively collected and summarized.The summarized results indicate that chemical-based ILs/DESs are superior to physical-based ILs/DESs for CO_(2)capture,especially those ILs have functionalized cation and anion,and superbase DESs;some of the superbase DESs have higher CO_(2)solubilities than those of ILs;the best physical-and chemical-based ILs,as well as physical-and chemicalbased DESs are[BMIM][BF4](4.20 mol kg^(-1)),[DETAH][Im](11.91 mol kg^(-1)),[L-Arg]-Gly 1:6(4.92 mol kg^(-1))and TBD-EG 1:4(12.90 mol kg^(-1)),respectively.Besides the original COSMO-RS mainly providing qualitative predictions,six corrected COSMO-RS models have been proposed to improve the prediction performance based on the experimental data,but only one model is with universal parameters.The newly determined experimental results were further used to verify the perditions of original and corrected COSMO-RS models.The comparison indicates that the original COSMO-RS qualitatively predicts CO_(2)solubility for some but not all ILs/DESs,while the quantitative prediction is incapable at all.The original COSMO-RS is capable to predict CO_(2)Henry’s constant qualitatively for both physical-based ILs and DESs,and quantitative prediction is only available for DESs.For the corrected COSMO-RS models,only the model with universal parameters provides quantitative predictions for CO_(2)solubility in physical-based DESs,while other corrected models always show large deviations(>83%)compared with the experimental CO_(2)Henry’s constants.展开更多
Efficient recycling technology for the rapid growth of spent lithium-ion batteries(LIBs)is essential to tackle the resources and environmental crisis.Hydrometallurgical approach has attracted extensive research due to...Efficient recycling technology for the rapid growth of spent lithium-ion batteries(LIBs)is essential to tackle the resources and environmental crisis.Hydrometallurgical approach has attracted extensive research due to its potential to reduce the consumption of energy and threat to the environment.However,the simultaneous realization of green,efficient and closed-loop recycling is still challenging.Herein,we report a closed-loop and highly efficient approach to recycle lithium cobalt oxide from spent LIBs based on a choline chloride:oxalic acid(ChCl:OA)type deep eutectic solvent(DES).An ultrafast leaching process is observed at 180°C for 10 s with no observable residues.The energy barrier during leaching is calculated to be 113.9 kJ/mol.Noteworthy,the solubility of cobalt ions can be reversibly tuned by simply adding/evaporating deionized water,thus avoiding the addition of precipitant and enabling the easy recovery of the leaching solvent for realizing a closed-loop recycling process.The simultaneous realization of high efficiency,green and closed-loop process is expected to push the DES into practical application for recycling the electrodes of LIBs.展开更多
Aqueous supercapacitors(SCs)have received considerable attention owing to the utilization of low-cost,non-flammable,and low-toxicity aqueous electrolytes thus could eliminate the safety and cost concerns,but their wid...Aqueous supercapacitors(SCs)have received considerable attention owing to the utilization of low-cost,non-flammable,and low-toxicity aqueous electrolytes thus could eliminate the safety and cost concerns,but their wide temperature range applications have generally suffered from frozen of electrolyte and insufficient ionic conductivity at low temperatures.Herein,we demonstrate the feasibility of using an unconventional Deep Eutectic Solvent(DES)based on H2O-Mg(ClO4)2·6 H2O binary system as electrolyte to construct all-climate aqueous carbon-based SC.This unconventional class DES completely base on inorganic substances and achieving simply mix inexpensive salts and water together at the right proportions.Attributed to the attractive feature of extremely low freeze temperature of-69℃,this electrolyte can enable the 1.8 V carbon-based SC to fully work at-40℃with outstanding cycling stability.This DES electrolyte comprising of a single salt and a single solvent without any additive will open up an avenue for developing simple and green electrolytes to construct all-climate SC.展开更多
Seabuckthorn seed meal(SSM) is a waste of oil extraction industry that rich in protein. In order to seek suitable protein extraction method, three different deep eutectic solvents(DESs)(including choline chlorideglyce...Seabuckthorn seed meal(SSM) is a waste of oil extraction industry that rich in protein. In order to seek suitable protein extraction method, three different deep eutectic solvents(DESs)(including choline chlorideglycerol, choline chloride-oxalic acid and choline chloride-urea) were developed for extracting protein from SSM and compared with alkaline. Result indicated that alkaline could effectively extract 56.9% protein from SSM and its protein content was 73.1%, higher than DES at 31.0%-41.4% and 64.3%-67.5%, respectively. However, compared to alkali, DES led to a product with less β-sheet, more β-turn, more essential amino acids, higher total amino acid content, especially choline chloride-urea which extracted protein showing an integrated and similar protein weight distribution compared to SSM. Also, this protein extracted chloride-urea showed a highest digestibility in vitro(by pepsin)(54.2%). These results indicated that choline chloride-urea extraction is better than alkaline extraction for SSM.展开更多
Poly(ethylene) oxide(PEO)-based electrolytes have been widely studied for solid-state lithium batteries while their ionic conductivity and lithium-ion transference number still need to be further improved.Herein, usin...Poly(ethylene) oxide(PEO)-based electrolytes have been widely studied for solid-state lithium batteries while their ionic conductivity and lithium-ion transference number still need to be further improved.Herein, using the combined experimental and theoretical approach, we demonstrate a novel, solidstate PEO-deep eutectic solvent(DES) electrolyte for the first time. We found that the in situ formation of DES can reduce the crystallinity of PEO matrix and more Li+ions can move freely owing to the weakened coordination between ether oxygens and Li-ions. Besides, we show that more Li+ions can be dissociated from Li salts in PEO-DES electrolyte using the molecular dynamics simulations. Such liquid-free PEO-DES electrolytes showed good ionic conductivity(2.1 × 10^(-4) S cm^(-1)) which is 160% higher than that of conventional PEO-Li TFSI(8.1 × 10^(-5) S cm^(-1)) electrolyte at 60 ℃. Additionally, the PEO-DES electrolyte showed 136% increase of Li-ion transference number(0.33) compared with ionic liquid-doped PEO-Li TFSI(0.14) at 60 ℃. Moreover, the PEO-DES exhibited good compatibility with Li metal and stable Li plating/stripping behavior with little morphology change of Li metal. This research also provides new insights into the enhancement mechanisms of novel polymer electrolytes, improving our fundamental understanding of critical challenges that have impeded the adoption of solid-state lithium metal batteries.展开更多
2-Ethylhexyl acrylate(2-EHA)is one of the most widely used acrylates in the polymer industry,which is synthesized via Fisher esterification that is limited by chemical equilibrium.To intensify the esterification proce...2-Ethylhexyl acrylate(2-EHA)is one of the most widely used acrylates in the polymer industry,which is synthesized via Fisher esterification that is limited by chemical equilibrium.To intensify the esterification process,in this work,reactive extraction concept is proposed,with halogen-free deep eutectic solvent(DES[Im:2PTSA])as dual solvent-catalyst that consists of imidazole(Im)and p-toluenesulfonamide(PTSA).The bifunctional effects of the DES[Im:2PTSA]are evaluated by thermodynamic analysis and experimental study.Favorable phase splitting is verified byσ-potential analysis predicted by COSMO-RS theory,combined with experiments,and the optimal acid-to-alcohol molar ratio is set to 1.2.The esterification kinetics is then experimentally determined and fitted using the molar-based and activity-based pseudo-homogeneous(PH)models,respectively.The activity-based PH model,that considers the bifunctional roles of the DES,proves to be more accurate with small RMSD of 0.0344.The stability of DES after recycling is validated to further confirm the industrial prospects of DES[Im:2PTSA]in 2-EHA production.展开更多
基金supported by the National Natural Science Foundation of China(22221005 and 22008033).
文摘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.
基金financially supported by Shanxi Province Natural Science Foundation of China(20210302123167)NSFC-Shanxi joint fund for coal-based low carbon(U1610223)Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering(2021SX-TD006).
文摘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.
基金the College Student Innovation and Entrepreneurship Training Program Project of Liaoning Province(202310148016)Doctoral Fund of Liaoning Province(201501105).
文摘A series of Lewis-acid deep eutectic solvents (DESs) were synthesized by stirring phosphoric acid and zincchloride as raw materials at 80 °C 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.
基金This work was supported by the National Natural Science Foundation of China[21978070]Natural Science Foundation of Henan[212300410032,232103810065]+2 种基金Key Research and Development Projects of Henan Province[221111320500]Program for Science&Technology Innovation Talents in Universities of Henan Province[20HASTIT034]Henan Province“Double First-Class”Project-Food Science and Technology.
文摘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.
基金Supported by Project of The Education Department of Fujian Province(JAT201227).
文摘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.
文摘As the demand for sustainable energy sources continues to rise,the need for efficient and reliable energy storage systems becomes crucial.In order to effectively store and distribute renewable energy,new and innovative solutions must be explored.This review examines the deep eutectic solvents(DESs)as a green,safe,and affordable solution for the electrochemical energy storage and conversion field,offering tremendous opportunities and a promising future.DESs are a class of environment-friendly solvents known for their low toxicity and unique properties,such as their good conductivity,high thermal stability,and nonflammability.This review explores the fundamentals,preparations,and various interactions that often predominate in the formation of DESs,the properties of DESs,and how DESs are better than traditional solvents involving cost-ineffective and unsafe organic electrolytes and ionic liquids as well as inefficient aqueous systems due to low energy density for electrochemical energy storage applications.Then,a particular focus is placed on the various electrochemical applications of DESs,including their role in the electrolytes in batteries/supercapacitors,electropolishing and electrodeposition of metals,synthesis of electrode materials,recycling of electrodes,and their potential for use in CO_(2)capture.The review concludes by exploring the challenges,research gaps,and future potential of DESs in electrochemical applications,providing a comprehensive overview,and highlighting key considerations for their design and use.
基金supported by the Key Area Research&Development Program of Guangdong Province(2020B0101070001)the National Natural Science Foundation of China(21978053,51508547)。
文摘Levulinic acid(LA)is one of the top-12 most promising biomass-based platform chemicals,which has a wide range of applications in a variety of fields.However,separation and purification of LA from aqueous solution or actual hydrolysate continues to be a challenge.Among various downstream separation technologies,liquid-liquid extraction is a low-cost,effective,and simple process to separate LA.The key breakthrough lies in the development of extractants with high extraction efficiency,good hydrophobicity,and low cost.In this work,three hydrophobic deep eutectic solvents(DESs)based on tri-n-octylamine(TOA)as hydrogen bond acceptor(HBA)and alcohols(butanol,2-octanol,and menthol)as hydrogen bond donors(HBDs)were developed to extract LA from aqueous solution.The molar ratios of HBD and HBA,extraction temperature,contact time,solution pH,and initial LA concentration,DES/water volume ratios were systematically investigated.Compared with 2-octanol-TOA and menthol-TOA DES,the butanol-TOA DES exhibited the superior extraction performance for LA,with a maximum extraction efficiency of 95.79±1.4%.Moreover,the solution pH had a great impact on the LA extraction efficiency of butanol-TOA(molar ratio=3:1).It is worth noting that the extraction equilibrium time was less than 0.5 h.More importantly,the butanol-TOA(3:1)DES possesses good extraction abilities for low,medium,and high concentrations of LA.
基金financially supported by the National Natural Science Foundation of China ( 21307028)Foundation of Henan province (202102310614)+1 种基金the Fundamental Research Funds for the Universities of Henan Province (NSFRF210428)the Foundation of Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow University (KJS2016)。
文摘Sinomenine is the main bio-active ingredient of Sinomenii Caulis and usually produced by solventextraction techniques. However, the extraction of sinomenine suffers from the lack of highly efficient and environmentally-benign solvents. In this work, deep eutectic solvents(DESs) based on fragrances were synthesized, hydrogen-bond donors(HBDs) and hydrogen-bond acceptors(HBAs) components of DESs were identified and their extraction ability for sinomenine was evaluated and the extraction conditions were optimized by single-factor and orthogonal design experiments. It was found that the hydrogen-bonding interaction between sinomenine and DESs was the main extraction driving force and there was no explicit relationship between the extraction ability and the hydrophobicity of the DESs. The DESs could be recycled and sinomenine could be recovered quantitatively via backextraction. High-purity sinomenine((95.0 ± 2.3)%) could be produced. These findings suggest that DESs are highly-effective solvents for the isolation of sinomenine and exhibit great potential for the extraction of other bio-active compounds.
基金financial support from the graduate council of the University of Tabriz,Tabriz,Iran.
文摘Important efforts have been made over the past years to improve the drug acts,which leads to the discovery of novel drug preparations and delivery systems.The optimal design of such processes requires a molecular-level understanding of the interactions between drug molecules and biological membranes.The thermodynamic investigation provides deep and complete knowledge of interactions and the choice of appropriate and suitable production compounds in pharmaceutical fields.Particularly,the analysis of drugs+co-solvents in aqueous media is the central issue in many types of research because they exert their impact by interacting with biological membranes.This work is aimed to measure the density and speed of sound for the thiamine hydrochloride in water+deep eutectic solvents(DESs)mixtures(choline chloride/urea,choline chloride/ethylene glycol and choline chloride/glycerol)at temperature range(293.15-308.15)K.By correlation of the evaluated parameters in some standard relations,the partial molar parameters i.e.apparent molar volumes,Vφ,m,and apparent molar isentropic compression,κ_(s,φ,m),are calculated.In addition,apparent molar isobaric expansion,E^(0)_(φ,m),and Hepler’s constant are computed from the density and speed of sound data.For fitting the experimental Vφ,m andκ_(s,φ,m)the Redlich-Meyer equation was employed that the important quantities;standard partial molar volume,V^(0)_(m),and partial molar isentropic compression,κφ,m0,were obtained.The thermodynamic analysis of the studied system also plays a crucial role in the pharmaceutical industry.
基金financially supported by the National Natural Science Foundation of China (21905069, U21A20307, 22208073)the Shenzhen Science and Technology Innovation Committee (ZDSYS20190902093220279, KQTD20170809110344233, GXWD20201230155427003-20200821181245001, GXWD20201230155427003-202008211 81809001, ZX20200151)the Department of Science and Technology of Guangdong Province (2020A1515110879)。
文摘The development of green solvents for enhancing aqueous solubility of drug curcumin remains a challenge. This study explores the enhancing effect of deep eutectic solvents(DESs) on the aqueous solubility of curcumin(CUR) via experiment and theoretical calculation. Choline chloride-based DESs with polyols 1,2-propanediol(1,2-PDO), 1,3-propanediol, ethylene glycol, and glycerol as hydrogen bond donors were prepared and used as co-solvents. The CUR aqueous solubility increased with increasing the DESs content at temperature of 303.15-318.15 K, especially in aqueous ChCl/1,2-PDO(mole ratio 1:4) solutions. The positive apparent molar volume values and reduced density gradient analysis confirmed the existence of strong interactions between CUR and solvent. The van der Waals interactions and hydrogen bonding coexisted in DESs monomer retained the stability of DESs structure after introducing CUR. Moreover,the lower interaction energy of DESs…CUR system than that of the counterpart DESs further proved the strong interaction between CUR and DESs. The lowest interaction energy of ChCl/1,2-PDO…CUR system indicated that this system was the most stable and ChCl/1,2-PDO was promising for CUR dissolution.This work provides efficient solvents for utilizing curcumin, contributing to a deep insight into the interactions between DES and CUR at the molecular level, and the role of DESs on enhancing drugs solubility.
基金support from the National Natural Science Foundation of China(Nos.52120105007,51834010)the National Science Fund for Distinguished Young Scholars(No.52222403).
文摘Fracturing fluid property play a critical role in developing unconventional reservoirs.Deep eutectic solvents(DESs)show fascinating potential for property improvement of clean fracturing fluids(CFFs)due to their low-price,low-toxicity,chemical stability and flexible designability.In this work,DESs were synthesized by mixing hydrogen bond acceptors(HBAs)and a given hydrogen bond donor(HBD)to explore their underlying influence on CFF properties based on the intermolecular interactions.The hydrogen-bonding,van der Waals and electrostatic interactions between DES components and surfactants improved the CFF properties by promoting the arrangement of surfactants at interface and enhancing the micelle network strength.The HBD enhanced the resistance of CFF for Ca^(2+) due to coordination-bonding interaction.The DESs composed of choline chloride(ChCl)and malonic acid show great enhancement for surface,rheology,temperature resistance,salt tolerance,drag reduction,and gel-breaking performance of CFFs.The DESs also improved the gel-breaking CFF-oil interactions,increasing the imbibition efficiencies to 44.2%in 74 h.Adjusting HBAs can effectively strengthen the intermolecular interactions(e.g.,HBA-surfactant and HBD-surfactant interactions)to improve CFF properties.The DESs developed in this study provide a novel strategy to intensify CFF properties.
基金support of the National Natural Science Foundation of China (21962008)Yunnan Province Excellent Youth Fund Project (202001AW070005)+1 种基金Candidate Talents Training Fund of Yunnan Province (2017PY269SQ,2018HB007)Yunnan Ten Thousand Talents Plan Young&Elite Talents Project (YNWR-QNBJ-2018-346)。
文摘Ni-Fe bimetallic electrodes are currently recognized as a kind of benchmark transition metal-based oxygen evolution reaction(OER)electrocatalysts.Facile synthesis of Ni-Fe bimetallic electrode materials with excellent catalytic activity and satisfied stability by a simple and low-cost route is still a big challenge.Herein,well-defined Ni-Fe nanoparticles in-situ developed on a planar Fe substrate(Ni-Fe NPs/Fe)is fabricated via a facile one-step galvanic replacement reaction(GRR)carried out in an Ethaline-based deep eutectic solvent(DES).The prepared Ni-Fe NPs/Fe exhibits outstanding OER performance,which needs an overpotential of only 319 mV to drive a current density of 10 mA cm^(-2),with a small Tafel slope of 41.2 mV dec^(-1) in 1.0 mol L^(-1) KOH,high mass activity(up to 319.78 A g^(-1) at an overpotential of 300 mV)and robust durability for 200 h.Impressively,the Ni-Fe bimetallic oxygen-evolution electrode obtained from the Ethaline-based DES is catalytically more active and durable than that of its counterpart derived from the 4.2 mol L^(-1) NaCl aqueous solution.The reason for this is mainly related to the different morphology and surface state of the Ni-Fe catalysts obtained from these different solvent environments,particularly for the differences in phy-chemical properties,active species formed and deposition kinetics,offered by the Ethaline-based DES.
基金financially supported by the National Natural Science Foundation of China (Nos. 21506080 and 21766007)Natural Science Foundation of Jiangsu Province (No. BK20150485)+1 种基金Advanced Talents of Jiangsu University (No. 15JDG053)A Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘Deep eutectic solvents(DESs) are a new class of green solvents analogous to ionic liquids due to their biodegradable capacity and low cost. However, the direct extractive desulfurization of diesel oil by DESs cannot meet the government’s standard. In this work, amphiphilic polyoxometalates were synthesized and characterized by FT-IR and mass spectrometry.The oxidative desulfurization results showed that benzothiophene(BT) could be completely removed by employing a [(CH)P(CH)]PMoO, DES(ChCl/2 Ac) and HOsystem. It was also found that the organic cation of catalysts played a positive role in oxidative desulfurization. The reaction conditions, such as reaction temperature and time, the amount of catalyst and DES and HO/S(O/S) molar ratio, were optimized. Different sulfides were tested to determine the desulfurization selectivity of the optimal reaction system, and it was found that 97.2% of dibenzothiophene(DBT) could be removed followed by 80.7% of 4-MDBT and 76.0% of 4,6-DMDBT. After reaction, the IR spectra showed that the catalyst [(CH)P(CH)]PMoOwas stable during the reaction process and the oxidative product was dibenzothiophene sulfone(DBTO). Furthermore, the catalyst can be regenerated and recycled for four runs with little loss of activity.
基金The financial support from National Natural Science Foundation of China(21776074,21576081,and 2181101120)is greatly acknowledged
文摘This review divides the acidic deep eutectic solvents(ADES) into Br?nsted and Lewis DES according to their diversity of acidic character.The hydrogen bond donors and halide salts for formulating an ADES are classified, the synthesis methods are described, and the physicochemical properties including freezing point, acidity, density, viscosity and conductivity are presented. Furthermore, the applications of Br?nsted acidic deep eutectic solvents(BADES) and Lewis acidic deep eutectic solvents(LADES) are overviewed, respectively, covering the fields in dissolution, extraction, organic reaction and metal electrodeposition. It is expected that the ADES has great potential to replace the pollutional mineral acid, expensive and unstable solid acid, and costly ionic liquid in many acid-employed chemical processes, thus meeting the demands of green chemistry.
基金financially supported by Carl Tryggers Stiftelse foundation(No.18:175)the financial support from the Swedish Energy Agency(P47500-1)+5 种基金K.C.Wang Education Foundation(No.GJTD-201804)the financial support from the National Natural Science Foundation of China(No.21890764)the financial supports from the National Natural Science Foundation of China(No.21838010)the financial support from the National Natural Science Foundation of China(No.21776276)the National Natural Science Foundation of China(21701024)the Foundation for Distinguished Young Talents in Higher Education of Fujian Province(GY-Z17067)
文摘The CO_(2)solubilities(including CO_(2)Henry’s constant)in physical-and chemical-based ILs/DESs and the COSMO-RS models describing these properties were comprehensively collected and summarized.The summarized results indicate that chemical-based ILs/DESs are superior to physical-based ILs/DESs for CO_(2)capture,especially those ILs have functionalized cation and anion,and superbase DESs;some of the superbase DESs have higher CO_(2)solubilities than those of ILs;the best physical-and chemical-based ILs,as well as physical-and chemicalbased DESs are[BMIM][BF4](4.20 mol kg^(-1)),[DETAH][Im](11.91 mol kg^(-1)),[L-Arg]-Gly 1:6(4.92 mol kg^(-1))and TBD-EG 1:4(12.90 mol kg^(-1)),respectively.Besides the original COSMO-RS mainly providing qualitative predictions,six corrected COSMO-RS models have been proposed to improve the prediction performance based on the experimental data,but only one model is with universal parameters.The newly determined experimental results were further used to verify the perditions of original and corrected COSMO-RS models.The comparison indicates that the original COSMO-RS qualitatively predicts CO_(2)solubility for some but not all ILs/DESs,while the quantitative prediction is incapable at all.The original COSMO-RS is capable to predict CO_(2)Henry’s constant qualitatively for both physical-based ILs and DESs,and quantitative prediction is only available for DESs.For the corrected COSMO-RS models,only the model with universal parameters provides quantitative predictions for CO_(2)solubility in physical-based DESs,while other corrected models always show large deviations(>83%)compared with the experimental CO_(2)Henry’s constants.
基金supported by the Talented Program of Guizhou University(702759203301)the Natural Science Foundation of Guizhou Science and Technology Department(QKHJC-ZK[2021]-YB257)。
文摘Efficient recycling technology for the rapid growth of spent lithium-ion batteries(LIBs)is essential to tackle the resources and environmental crisis.Hydrometallurgical approach has attracted extensive research due to its potential to reduce the consumption of energy and threat to the environment.However,the simultaneous realization of green,efficient and closed-loop recycling is still challenging.Herein,we report a closed-loop and highly efficient approach to recycle lithium cobalt oxide from spent LIBs based on a choline chloride:oxalic acid(ChCl:OA)type deep eutectic solvent(DES).An ultrafast leaching process is observed at 180°C for 10 s with no observable residues.The energy barrier during leaching is calculated to be 113.9 kJ/mol.Noteworthy,the solubility of cobalt ions can be reversibly tuned by simply adding/evaporating deionized water,thus avoiding the addition of precipitant and enabling the easy recovery of the leaching solvent for realizing a closed-loop recycling process.The simultaneous realization of high efficiency,green and closed-loop process is expected to push the DES into practical application for recycling the electrodes of LIBs.
基金financially supported by the DNL Cooperation Fund,Chinese Academy of Sciences(DNL180307)Natural Science Foundation of Gansu Province(18JR3RA159)。
文摘Aqueous supercapacitors(SCs)have received considerable attention owing to the utilization of low-cost,non-flammable,and low-toxicity aqueous electrolytes thus could eliminate the safety and cost concerns,but their wide temperature range applications have generally suffered from frozen of electrolyte and insufficient ionic conductivity at low temperatures.Herein,we demonstrate the feasibility of using an unconventional Deep Eutectic Solvent(DES)based on H2O-Mg(ClO4)2·6 H2O binary system as electrolyte to construct all-climate aqueous carbon-based SC.This unconventional class DES completely base on inorganic substances and achieving simply mix inexpensive salts and water together at the right proportions.Attributed to the attractive feature of extremely low freeze temperature of-69℃,this electrolyte can enable the 1.8 V carbon-based SC to fully work at-40℃with outstanding cycling stability.This DES electrolyte comprising of a single salt and a single solvent without any additive will open up an avenue for developing simple and green electrolytes to construct all-climate SC.
基金the financial support from the National Natural Science Foundation of China (No. 31201416)Science and Technology Research Program of Guangdong Province (No. 2017A01010502)。
文摘Seabuckthorn seed meal(SSM) is a waste of oil extraction industry that rich in protein. In order to seek suitable protein extraction method, three different deep eutectic solvents(DESs)(including choline chlorideglycerol, choline chloride-oxalic acid and choline chloride-urea) were developed for extracting protein from SSM and compared with alkaline. Result indicated that alkaline could effectively extract 56.9% protein from SSM and its protein content was 73.1%, higher than DES at 31.0%-41.4% and 64.3%-67.5%, respectively. However, compared to alkali, DES led to a product with less β-sheet, more β-turn, more essential amino acids, higher total amino acid content, especially choline chloride-urea which extracted protein showing an integrated and similar protein weight distribution compared to SSM. Also, this protein extracted chloride-urea showed a highest digestibility in vitro(by pepsin)(54.2%). These results indicated that choline chloride-urea extraction is better than alkaline extraction for SSM.
基金financially supported by the Samsung Advanced Institute of Technology(SAIT)’s Global Research Outreach(GRO)programthe China Scholarship Council(CSC)for the financial supportThe NMR measurement was conducted under the Laboratory Directed Research and Development Program(LDRD)at Pacific Northwest National Laboratory(PNNL),a multiprogram national laboratory operated by Battelle for the U.S.Department of Energy and was performed at the Environmental Molecular Sciences Laboratory(EMSL),a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL。
文摘Poly(ethylene) oxide(PEO)-based electrolytes have been widely studied for solid-state lithium batteries while their ionic conductivity and lithium-ion transference number still need to be further improved.Herein, using the combined experimental and theoretical approach, we demonstrate a novel, solidstate PEO-deep eutectic solvent(DES) electrolyte for the first time. We found that the in situ formation of DES can reduce the crystallinity of PEO matrix and more Li+ions can move freely owing to the weakened coordination between ether oxygens and Li-ions. Besides, we show that more Li+ions can be dissociated from Li salts in PEO-DES electrolyte using the molecular dynamics simulations. Such liquid-free PEO-DES electrolytes showed good ionic conductivity(2.1 × 10^(-4) S cm^(-1)) which is 160% higher than that of conventional PEO-Li TFSI(8.1 × 10^(-5) S cm^(-1)) electrolyte at 60 ℃. Additionally, the PEO-DES electrolyte showed 136% increase of Li-ion transference number(0.33) compared with ionic liquid-doped PEO-Li TFSI(0.14) at 60 ℃. Moreover, the PEO-DES exhibited good compatibility with Li metal and stable Li plating/stripping behavior with little morphology change of Li metal. This research also provides new insights into the enhancement mechanisms of novel polymer electrolytes, improving our fundamental understanding of critical challenges that have impeded the adoption of solid-state lithium metal batteries.
基金The financial support from National Natural Science Foundation of China(21776074,21861132019 and 21978096)is greatly acknowledged
文摘2-Ethylhexyl acrylate(2-EHA)is one of the most widely used acrylates in the polymer industry,which is synthesized via Fisher esterification that is limited by chemical equilibrium.To intensify the esterification process,in this work,reactive extraction concept is proposed,with halogen-free deep eutectic solvent(DES[Im:2PTSA])as dual solvent-catalyst that consists of imidazole(Im)and p-toluenesulfonamide(PTSA).The bifunctional effects of the DES[Im:2PTSA]are evaluated by thermodynamic analysis and experimental study.Favorable phase splitting is verified byσ-potential analysis predicted by COSMO-RS theory,combined with experiments,and the optimal acid-to-alcohol molar ratio is set to 1.2.The esterification kinetics is then experimentally determined and fitted using the molar-based and activity-based pseudo-homogeneous(PH)models,respectively.The activity-based PH model,that considers the bifunctional roles of the DES,proves to be more accurate with small RMSD of 0.0344.The stability of DES after recycling is validated to further confirm the industrial prospects of DES[Im:2PTSA]in 2-EHA production.