Commercial carbonate electrolytes suffer from ion transport difficulty in bulk electrolytes and interphase at low temperatures,bringing challenges to the application of lithium-ion batteries(LIBs)at low temperatures.H...Commercial carbonate electrolytes suffer from ion transport difficulty in bulk electrolytes and interphase at low temperatures,bringing challenges to the application of lithium-ion batteries(LIBs)at low temperatures.Herein,the ester solvent of methyl propionate(MP)with low melting point and low viscosity was used to tackle ion transport difficulty in electrolytes.Fluorinated ester was further added to accelerate interfacial transport through intermolecular interactions.The influence of fluorinated esters with different fluorination degrees on the solvation structure of electrolytes and the performance of batteries was further studied.As a result,methyl pentafluoropropionate(M5F)with five fluorine atoms was selected for its optimal interactions with both Li+and MP solvent in the primary solvation structure,contributing to desired solvation structure for fast interfacial transport.The LiFePO_(4)(LFP)||graphite cell with LiFSI-MP-M5F electrolyte exhibited a high cyclability of 85.8%after 120 cycles and retained 81.2%of room-temperature capacity when charged and discharged at−30℃.1 Ah LFP||graphite pouch cell with high cathode loading(20 mg/cm^(2))in LiFSI-MP-M5F electrolyte exhibited 0.85 Ah capacity when charged and discharged at−20℃.This work provides a guidance for electrolyte design by synergistic fluorinated and non-fluorinated solvents for LIBs at low-temperature application.展开更多
The impurities and structural cracks within spent graphite(SG)in lithium-ion battery anodes hamper lithium-ion intercalation and extraction after successive charge-discharge operations,thereby yielding poor lithium st...The impurities and structural cracks within spent graphite(SG)in lithium-ion battery anodes hamper lithium-ion intercalation and extraction after successive charge-discharge operations,thereby yielding poor lithium storage behavior.Herein,low-viscosity natural deep eutectic solvent(NDES)composed of citric acid(CA)and betaine hydrochloride was employed to remove the organic impurities in SG via a one-step benign process involving hydrogen bonds and electrostatic interactions at mild conditions of 80℃ for only 30 min.After NDES leaching under optimal conditions(molar ratio of CA to betaine hydrochloride=3:1,80℃,30 min),the as-obtained sample(denoted as BG-3)exhibited an extremely clean surface,moderately enlarged interlayer distance,and more structural defects at the edge of graphite lamellae.These features facilitated lithium-ion intercalation and withdrawal,bestowing BG-3 with remarkable activity in lithium-ion battery(LIB)recycling.For instance,BG-3 delivered a capacity of 438.6 mAh g^(-1) at a current density of 0.1 A g^(-1).Its capacity retention reached 97.9%,accompanied by a Coulombic efficiency of 99.1%,upon completing 100 cycles.A molecular dynamics simulation was employed to illuminate the regeneration mechanism for anode graphite from a theoretical perspective.It revealed that NDES exhibits lower binding energy with all contaminants compared to graphite,which is favorable for NDES to eliminate impurities from graphite surfaces.This study unveils a method of recycling SG from retired LIBs by a short eco-friendly process,providing a competitive blueprint to address the shortage of battery-grade anode graphite and to achieve carbon neutrality.展开更多
Lithium-ion batteries(LIBs)face significant limitations in low-temperature environments,with the slow interfacial de-solvation process and the hindered Li+transport through the interphase layer emerging as key obstacl...Lithium-ion batteries(LIBs)face significant limitations in low-temperature environments,with the slow interfacial de-solvation process and the hindered Li+transport through the interphase layer emerging as key obstacles beyond the issue of ionic conductivity.This investigation unveils a novel formulation that constructs an anion-rich solvation sheath within strong solvents,effectively addressing all three of these challenges to bolster low-temperature performance.The developed electrolyte,characterized by an enhanced concentration of contact ion pairs(CIPs)and aggregates(AGGs),facilitates the formation of an inorganic-rich interphase layer on the anode and cathode particles.This promotes de-solvation at low temperatures and stabilizes the electrode-electrolyte interphase.Full cells composed of LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM622)and graphite,when equipped with this electrolyte,showcase remarkable cycle stability and capacity retention,with 93.3% retention after 500 cycles at room temperature(RT)and 95.5%after 120 cycles at -20℃.This study validates the utility of the anion-rich solvation sheath in strong solvents as a strategy for the development of low-temperature electrolytes.展开更多
The rising need for efficient and sustainable energy storage systems has led to increased interest in the use of advanced electrolytes consisting of deep eutectic solvents(DESs) and ionic liquids(ILs).These electrolyt...The rising need for efficient and sustainable energy storage systems has led to increased interest in the use of advanced electrolytes consisting of deep eutectic solvents(DESs) and ionic liquids(ILs).These electrolytes are appealing candidates for supercapacitors,next-generation lithium-ion batteries,and different energy storage systems because of their special features including non-flammability,low volatility,lowtoxicity,good electrochemical stability,and good thermal and chemical stability.This review explores the advantages of the proposed electrolytes by examining their potential to address the critical challenges in lithium battery technology,including safety concerns,energy density limitations,and operational stability.To achieve this,a comprehensive overview of the lithium salts commonly employed in rechargeable lithium battery electrolytes is presented.Moreover,key physicochemical and functional attributes of ILs and DESs,such as electrochemical stability,ionic conductivity,nonflammability,and viscosity are also discussed with a focus on how these features impact battery performance.The integration of lithium salts with ILs and DESs in modern lithium battery technologies,including lithium-ion(Li-ion) batteries,lithium-oxygen(Li-O_(2)) batteries,and lithium-sulfur(Li-S) batteries,are further examined in the study.Various electrochemical performance metrics including cycling stability,charge/discharge profiles,retention capacity and battery's couiombic efficiency(CE) are also analyzed for the above-mentioned systems.By summarizing recent advances and challenges,this review also highlights the potential of electrolytes consisting of DESs and ILs to enhance energy density,durability,and safety in future energy storage applications.Additionally future research directions,including the molecular optimization of ILs and DESs,optimizing lithium salt compositions,and developing scalable synthesis methods to accelerate their practical implementation in next-generation energy storage applications are also explored.展开更多
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 ...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.展开更多
The chain conformation of polymers in binary solvent mixtures is a key issue in the study of functional soft matter and lies at the heart of various applications such as smart soft materials.Based on a minimal lattice...The chain conformation of polymers in binary solvent mixtures is a key issue in the study of functional soft matter and lies at the heart of various applications such as smart soft materials.Based on a minimal lattice model,we employ Monte Carlo(MC)simulation to systematically investigate the effects of solvent qualities on the conformation of a single homopolymer chain in binary mixed solvents.We also perform calculations using a Flory-type mean-field theory.We focus on how the introduction of a second solvent B affects the dependence of chain conformation on the quality of solvent A.We mainly examine the effects of the composition of solvent B,denoted by x,and the interactions between the two solvents.First,when x is low,the mean-square chain radius of gyration exhibits qualitatively similar behaviors to those in an individual solvent A,with a slight chain contraction when solvent A is very good.Second,in equal-molar mixtures with x=0.5,a homopolymer chain collapses when solvent A is either poor or very good,while expands at intermediate qualities.Lastly,at large x,a chain undergoes a coil-to-globule transition with the increasing quality of solvent A when solvent B is good,but mainly adopts the collapsed conformation when solvent B is poor.Our findings not only improve our understanding on the chain conformation in binary solvent mixtures,but also provide valuable guidance on the rational design of stimuli-responsive polymeric materials.展开更多
This study explores green and low-viscosity deep eutectic solvents(DESs) for the efficient extraction of quinoline(QUI) from wash oil.The hydrogen bond donors and acceptors constituting DESs were initially screened ba...This study explores green and low-viscosity deep eutectic solvents(DESs) for the efficient extraction of quinoline(QUI) from wash oil.The hydrogen bond donors and acceptors constituting DESs were initially screened based on thermodynamic properties predicted by the conductor-like screening model for real solvents(COSMO-RS),followed by further selection considering the viscosity and cost of the formed DESs.Phase equilibrium experiments showed that the DES composed of triethylmethylammonium chloride and formic acid exhibited the best extraction performance among the selected candidates.Key extraction parameters were optimized experimentally,achieving a maximum QUI extraction efficiency of 97.18% under mild conditions.Molecular dynamics simulations revealed that the interactions between quaternary ammonium cations and QUI play a crucial role in the extraction mechanism.This study provides insights into the use of DESs for QUI extraction and demonstrates their potential for application to other coal tar derivatives.展开更多
Green extraction of bioactive components from natural sources has been a hot topic in the field of chemistry and biology.As a kind of green solvents,deep eutectic solvents(DESs)have unique advantages in the extraction...Green extraction of bioactive components from natural sources has been a hot topic in the field of chemistry and biology.As a kind of green solvents,deep eutectic solvents(DESs)have unique advantages in the extraction of bioactive substances.In recent years,as a new subgroup of DESs,the switchable deep eutectic solvents(SDESs)can realize reversible phase switching between hydrophobic and hydrophilic by external driving forces(CO_(2)/p H/temperature),allowing for the extraction of different polar components while avoiding the problem of difficult recovery of DESs.The application of SDESs reduces the consumption of large amounts of organic solvents during the extraction process,thereby promoting sustainability.In the meanwhile,it presents an advantage over traditional extraction methods in preserving product activity.Based on the recent researches on SDESs,this work summarized the composition,driving factors,and conversion mechanism of SDESs.The applications of SDESs in the extraction of natural products were primarily highlighted to provide a reference for future research.展开更多
Candida albicans is one of the most common pathogens causing invasive fungal infections,with a mortality rate of up to 20%-50%.Amphotericin B(AmB),a biopharmaceutics classification system(BCS)IV drug,significantly inh...Candida albicans is one of the most common pathogens causing invasive fungal infections,with a mortality rate of up to 20%-50%.Amphotericin B(AmB),a biopharmaceutics classification system(BCS)IV drug,significantly inhibits Candida albicans.AmB is primarily administered via oral and intravenous infusion,but severe infusion adverse effects,nephrotoxicity,and potential hepatotoxicity limit its clinical application.Deep eutectic solvents(DESs),with excellent solubilization ability and skin permeability,are attractive for transdermal delivery.Herein,we used DESs to deliver AmB for antifungal therapy transdermally.We first prepared and characterized DESs with different stoichiometric ratios of choline(Ch)and geranate(Ge).DESs increased the solubility of AmB by a thousand-fold.In vitro and in vivo,skin permeation studies indicated that DES_(1:2)(Ch and Ge in 1:2 ratio)had the most outstanding penetration and delivered fluorescence dye to the dermis layer.Then,DES_(1:2)-AmB was prepared and in vitro antifungal tests demonstrated that DES_(1:2)-AmB had superior antifungal effects compared to AmB and DES_(1:2).Furthermore,DES_(1:2)-AmB was skin-irritating and biocompatible.In conclusion,DES-AmB provides a new and effective therapeutic solution for fungal infections.展开更多
Ionic liquids (ILs) and deep eutectic solvents (DESs) as green solvents have attracted dramatic attention recently due to their highly tunable properties. However, traditional experimental screening methods are ineffi...Ionic liquids (ILs) and deep eutectic solvents (DESs) as green solvents have attracted dramatic attention recently due to their highly tunable properties. However, traditional experimental screening methods are inefficient and resource-intensive. The article provides a comprehensive overview of various ML algorithms, including artificial neural network (ANN), support vector machine (SVM), random forest (RF), and gradient boosting trees (GBT), etc., which have demonstrated exceptional performance in handling complex and high-dimensional data. Furthermore, the integration of ML with quantum chemical calculations and conductor-like screening model-real solvent (COSMO-RS) has significantly enhanced predictive accuracy, enabling the rapid screening and design of novel solvents. Besides, recent ML applications in the prediction and design of ILs and DESs focused on solubility, melting point, electrical conductivity, and other physicochemical properties become more and more. This paper emphasizes the potential of ML in solvent design, overviewing an efficient approach to accelerate the development of sustainable and high-performance materials, providing guidance for their widespread application in a variety of industrial processes.展开更多
The development of low-energy consumption and environmentally friendly electrodeposition of metal/alloy films or coatings is presently one of the primary topics for the research community.For this purpose,deep eutecti...The development of low-energy consumption and environmentally friendly electrodeposition of metal/alloy films or coatings is presently one of the primary topics for the research community.For this purpose,deep eutectic solvents(DESs)are valued as electrolytes for their advantages of low operating temperature and wide electrochemical windows.At present,there is large amount of literature on this emerging field,but there are no specialized reviews of these studies.Here,after a brief introduction of DESs’concept and history,we comprehensively reviewed the lastest progress on the metal/alloy electrodeposition in DESs.Additionally,we discussed the key influence factors of the electrodeposition process and analyzed the corresponding mechanisms.Based on these,we emphasized the importance of the establishment of predictive models for dealing with the challenges in large-scale applications.展开更多
Recently, deep eutectic solvents (DES) have received great attention in assisting water flooding and surfactant flooding to improve oil recovery because they can reduce the interfacial tension (IFT) between oil and wa...Recently, deep eutectic solvents (DES) have received great attention in assisting water flooding and surfactant flooding to improve oil recovery because they can reduce the interfacial tension (IFT) between oil and water, inhibit surfactant adsorption, and change the wettability of rock. However, the effects of DES on the wettability of rock surface have not been thoroughly investigated in the reported studies. In this study, the effects of various DES samples on the wettability of sandstone samples are investigated using the Amott wettability measurement method. Three DES samples and several DES solutions and DES-surfactant solutions are firstly synthesized. Then, the wettability of the sandstone samples is measured using pure saline water, DES solutions, and DES-surfactant solutions, respectively. The effects of the DES samples on the wettability of the sandstone samples are investigated by comparing the measured wettability parameters, including oil displacement ratio (I_(o)), water displacement ratio (I_(w)), and wettability index (I_(A)). The Berea rock sample used in this study is weakly hydrophilic with I_(o), I_(w), and I_(A) of 0.318, 0.032, and 0.286, respectively. Being processed by the prepared DES samples, the wettability of the Berea sandstone samples is altered to hydrophilic (0.7 > I_(A) > 0.3) by increasing I_(w) but lowering Io. Similarly, DES-surfactant solutions can also modify the wettability of the Berea sandstone samples from weakly hydrophilic to hydrophilic. However, some DES-surfactant solutions can not only increase I_(w) but also increase I_(o), suggesting that the lipophilicity of those sandstone samples will be improved by the DES-surfactant solutions. In addition, micromodel flooding tests confirm the promising performance of a DES-surfactant solution in improving oil recovery and altering wettability. Moreover, the possible mechanisms of DES and DES-surfactant solutions in altering the wettability of the Berea sandstone samples are proposed. DES samples may improve the hydrophilicity by forming hydrogen bonds between rock surface and water molecules. For DES-surfactant solutions, surfactant micelles can capture oil molecules to improve the lipophilicity of those sandstone samples.展开更多
H_(2)S in natural gas and other industrial gas is seriously harmful to human health,environmental protection and the downstream industries.Efficient purification of H_(2)S containing gas is the basic process in the ch...H_(2)S in natural gas and other industrial gas is seriously harmful to human health,environmental protection and the downstream industries.Efficient purification of H_(2)S containing gas is the basic process in the chemical industry.Benefiting from multiple advantages,deep eutectic solvents(DES)can be used as tailor-made green solvents,and have been booming in the fields of harmful gas removal and fuel oil desulfurization.Furthermore,significant scientific research of DES in desulfurization and purification of natural gas has accelerated the process of its practical application.This paper systematically summarizes and analyzes the removal mechanism,impact factors and challenges of DES as emerging green solvent in H_(2)S absorption and conversion.Strategies on H_(2)S removal by DES generally fall into two categories:physical absorption and chemical conversion.Although the chemical conversion of H_(2)S by DES has been less studied compared with the physical absorption,it presents great application potential.At present,the research on H_(2)S removal by DES is still in the initial stage.Therefore,it is necessary to further study the mechanism of H_(2)S removal and construct the relationship between structural properties and desulfurization performance of DES,thereby to solve the issues of sulfur blockage and low quality of sulfur paste which is suffered by conventional liquid redox desulfurization solvent system.Additionally,the methods for efficient solvent regeneration and recycling remain to be explored out to promote the practical application of iron-based DES in the field of gas desulfurization.展开更多
Reaction crystallization method is a common cocrystal synthesis approach attributed to the advantage of avoiding individual crystallization of insoluble components,but faces the defects of soluble components precipita...Reaction crystallization method is a common cocrystal synthesis approach attributed to the advantage of avoiding individual crystallization of insoluble components,but faces the defects of soluble components precipitated due to organic solvent volatilization and the formation of unwanted solvates.Our group recently proposed a slurry method based on deep eutectic solvents(DESs)for cocrystal synthesis,which is green,safe and can avoid solvate formation.However,some reactions only produce insoluble raw materials rather than cocrystals due to insufficient activity of the soluble cocrystal co-formers in DESs.Herein,combining the dual benefits of the two methods,a novel reaction crystallization method based on DESs was proposed and employed for cocrystal synthesis of nicotinamide,carbamazepine and theophylline,which can prevent individual crystallization,unwanted solvate formation,and soluble component precipitation,providing a promising alternative for green and efficient synthesis of cocrystals.展开更多
Electrolyte engineering with fluoroethers as solvents offers promising potential for high-performance lithium metal batteries.Despite recent progresses achieved in designing and synthesizing novel fluoroether solvents...Electrolyte engineering with fluoroethers as solvents offers promising potential for high-performance lithium metal batteries.Despite recent progresses achieved in designing and synthesizing novel fluoroether solvents,a systematic understanding of how fluorination patterns impact electrolyte performance is still lacking.We investigate the effects of fluorination patterns on properties of electrolytes using fluorinated 1,2-diethoxyethane(FDEE)as single solvents.By employing quantum calculations,molecular dynamics simulations,and interpretable machine learning,we establish significant correlations between fluorination patterns and electrolyte properties.Higher fluorination levels enhance FDEE stability but decrease conductivity.The symmetry of fluorination sites is critical for stability and viscosity,while exerting minimal influence on ionic conductivity.FDEEs with highly symmetric fluorination sites exhibit favorable viscosity,stability,and overall electrolyte performance.Conductivity primarily depends on lithium-anion dissociation or association.These findings provide design principles for rational fluoroether electrolyte design,emphasizing the trade-offs between stability,viscosity,and conductivity.Our work underscores the significance of considering fluorination patterns and molecular symmetry in the development of fluoroether-based electrolytes for advanced lithium batteries.展开更多
Efficient recognition and selective capture of NH_(3)is not only beneficial for increasing the productivity of the synthetic NH_(3)industry but also for reducing air pollution.For this purpose,a group of deep eutectic...Efficient recognition and selective capture of NH_(3)is not only beneficial for increasing the productivity of the synthetic NH_(3)industry but also for reducing air pollution.For this purpose,a group of deep eutectic solvents(DESs)consisting of glycolic acid(GA)and phenol(PhOH)with low viscosities and multiple active sites was rationally designed in this work.Experimental results show that the GA^(+)PhOH DESs display extremely fast NH_(3)absorption rates(within 51 s for equilibrium)and high NH_(3)solubility.At 313.2 K,the NH_(3)absorption capacities of GA^(+)PhOH(1:1)reach 6.75 mol/kg(at 10.7 kPa)and 14.72 mol/kg(at 201.0 kPa).The NH_(3)solubility of GA^(+)PhOH DESs at low pressures were minimally changed after more than 100 days of air exposure.In addition,the NH_(3)solubility of GA^(+)PhOH DESs remain highly stable in 10 consecutive absorption-desorption cycles.More importantly,NH_(3)can be selectively captured by GA^(+)PhOH DESs from NH_(3)/CO_(2)/N_(2)and NH_(3)/N_(2)/H_(2)mixtures.1H-NMR,Fourier transform infrared and theoretical calculations were performed to reveal the intrinsic mechanism for the efficient recognition of NH_(3)by GA^(+)PhOH DESs.展开更多
Replacement of volatile organic compounds （VOCs） by greener or more environmentally sustainable solvents is becoming increasingly important due to the increasing health and environmental concerns as well as economic...Replacement of volatile organic compounds （VOCs） by greener or more environmentally sustainable solvents is becoming increasingly important due to the increasing health and environmental concerns as well as economic pressures associated with VOCs. Solvents that are derived from biomass, namely bio-derived solvents, are a type of green solvent that have attracted intensive investigations in recent years because of their advantages over con- ventional VOCs, such as low toxicity, biodegradability and renewability. This review aims to summarize the use of bio-derived solvents in solvent extraction applications, with special emphasis given to utilization of biodiesels and terpenes. Compared with the conventional VOCs, the overall performance of these bio-derived solvents is comparable in terms of extraction yields and selectivity for natural product extraction and no difference was found for metal extraction. To date most researchers have focused on laboratory scale thermodynamics studies. Future work is required to develop and test new bio-derived solvents and understand the kinetic performance as well as solvent extraction nilnt nlant studies.展开更多
Deep eutectic solvents(DESs)have drawn considerable attention as a new type of green solvent since they were reported.Subsequent studies have shown that DESs have the potential to be used as“designable”solvents,whic...Deep eutectic solvents(DESs)have drawn considerable attention as a new type of green solvent since they were reported.Subsequent studies have shown that DESs have the potential to be used as“designable”solvents,which means that the precursors of DESs with different structures and properties can be screened to customize DESs for specific functions.Researchers have found that during the sample preparation process involving DESs,the specific properties of some“smart”DESs can be switched by directing external driving forces,leading to a reversible phase transition of the target solution.These"smart"DESs are called switchable deep eutectic solvents(SDESs).The advent of SDES simplifies the sample pretreatment steps,reduces the use of organic solvents,and makes solvents easy to recycle,which matches the concept of green and sustainable chemistry.Compared with the number of previous experimental studies,the reviews and summaries on SDESs are rare.Therefore,this review made a summary of the concept and research progress of SDESs based on some related works in the past decade,including composition and type,characterization,switching mechanism,etc.It is expected to provide a certain reference and guidance for the subsequent in-depth research of SDESs in the analytical sample pretreatment.展开更多
Biomass is renewable, abundant, cheap, biocompatible, and biodegradable materials and has been used to produce chemicals, materials,energy, and fuels. However, most of the biomass, especially most of the biomass polym...Biomass is renewable, abundant, cheap, biocompatible, and biodegradable materials and has been used to produce chemicals, materials,energy, and fuels. However, most of the biomass, especially most of the biomass polymers are not soluble in common solvents, which hinders their pretreatment and conversion. Deep eutectic solvents(DESs) are environmental-friendly, cheap, and highly tunable, with high solubility,which renders them potential applications in biomass pretreatment and conversion. They could be used as solvents or catalysts and so on. This paper intends to review the application of DESs for the pretreatment of biomass and conversion of biomass to value-added products. We focus on the following topics related to biomass and DESs:(1) DESs for the pretreatment of biomass;(2) DESs for the dissolution and separation of biomass or extraction of chemicals from biomass;(3) DESs for biomass conversion;(4) Drawbacks, and recyclability of DESs for pretreatment and conversion of biomass.展开更多
Despite the significance of hydrogen bonding in deep eutectic solvents（DESs） for desulfurization processes, little is understood about the relationship between the DES composition, hydrogen-bonding strength, and oxi...Despite the significance of hydrogen bonding in deep eutectic solvents（DESs） for desulfurization processes, little is understood about the relationship between the DES composition, hydrogen-bonding strength, and oxidative desulfurization activity. In this study, a new family of caprolactam-based acidic DESs was prepared with different molar ratios of caprolactam and oxalic acid. The prepared DESs were characterized by differential scanning calorimetry, Fourier transform infrared spectroscopy, 1 H nuclear magnetic resonance, and thermogravimetric analyses. These DESs were employed for oxidative desulfurization reactions and the desulfurization efficiency was found to vary regularly with the DES composition. The factors influencing the removal of dibenzothiophene were systematically investigated and the desulfurization efficiency of the caprolactam-based acidic DESs reached as high as 98% under optimal conditions. The removal of different sulfur compounds followed the order： dibenzothiophene 4,6-dimethyldibenzothiophene benzothiophene. The combined experimental data and characterization results revealed that the oxidative desulfurization efficiency of the system was influenced by the hydrogen bonding interactions with the DES, which can be optimized by adjusting the DES composition. These findings regarding hydrogen bonding in DESs provide new insight for better understanding of the mechanism of diesel deep desulfurization processes.展开更多
基金supported by the National Key R&D Program of China(No.2022YFB3803400)National Natural Science Foundation of China(Nos.52102054,52020105010,51927803,52188101 and 52072378)+1 种基金Liaoning Province Science and Technology Planning Project(No.2022-BS-007)Fujian Science and Technology Program(No.2023T3025).
文摘Commercial carbonate electrolytes suffer from ion transport difficulty in bulk electrolytes and interphase at low temperatures,bringing challenges to the application of lithium-ion batteries(LIBs)at low temperatures.Herein,the ester solvent of methyl propionate(MP)with low melting point and low viscosity was used to tackle ion transport difficulty in electrolytes.Fluorinated ester was further added to accelerate interfacial transport through intermolecular interactions.The influence of fluorinated esters with different fluorination degrees on the solvation structure of electrolytes and the performance of batteries was further studied.As a result,methyl pentafluoropropionate(M5F)with five fluorine atoms was selected for its optimal interactions with both Li+and MP solvent in the primary solvation structure,contributing to desired solvation structure for fast interfacial transport.The LiFePO_(4)(LFP)||graphite cell with LiFSI-MP-M5F electrolyte exhibited a high cyclability of 85.8%after 120 cycles and retained 81.2%of room-temperature capacity when charged and discharged at−30℃.1 Ah LFP||graphite pouch cell with high cathode loading(20 mg/cm^(2))in LiFSI-MP-M5F electrolyte exhibited 0.85 Ah capacity when charged and discharged at−20℃.This work provides a guidance for electrolyte design by synergistic fluorinated and non-fluorinated solvents for LIBs at low-temperature application.
基金supported by the National Natural Science Foundation of China(Project Nos.22372051 and 21406044)Australian Research Council/Discovery Early Career Researcher Award(DECRA)funding scheme(DE230100180).
文摘The impurities and structural cracks within spent graphite(SG)in lithium-ion battery anodes hamper lithium-ion intercalation and extraction after successive charge-discharge operations,thereby yielding poor lithium storage behavior.Herein,low-viscosity natural deep eutectic solvent(NDES)composed of citric acid(CA)and betaine hydrochloride was employed to remove the organic impurities in SG via a one-step benign process involving hydrogen bonds and electrostatic interactions at mild conditions of 80℃ for only 30 min.After NDES leaching under optimal conditions(molar ratio of CA to betaine hydrochloride=3:1,80℃,30 min),the as-obtained sample(denoted as BG-3)exhibited an extremely clean surface,moderately enlarged interlayer distance,and more structural defects at the edge of graphite lamellae.These features facilitated lithium-ion intercalation and withdrawal,bestowing BG-3 with remarkable activity in lithium-ion battery(LIB)recycling.For instance,BG-3 delivered a capacity of 438.6 mAh g^(-1) at a current density of 0.1 A g^(-1).Its capacity retention reached 97.9%,accompanied by a Coulombic efficiency of 99.1%,upon completing 100 cycles.A molecular dynamics simulation was employed to illuminate the regeneration mechanism for anode graphite from a theoretical perspective.It revealed that NDES exhibits lower binding energy with all contaminants compared to graphite,which is favorable for NDES to eliminate impurities from graphite surfaces.This study unveils a method of recycling SG from retired LIBs by a short eco-friendly process,providing a competitive blueprint to address the shortage of battery-grade anode graphite and to achieve carbon neutrality.
基金the National Natural Science Foundation of China(No.22279070[L.Wang]and U21A20170[X.He])the Ministry of Science and Technology of China(No.2019YFA0705703[L.Wang])。
文摘Lithium-ion batteries(LIBs)face significant limitations in low-temperature environments,with the slow interfacial de-solvation process and the hindered Li+transport through the interphase layer emerging as key obstacles beyond the issue of ionic conductivity.This investigation unveils a novel formulation that constructs an anion-rich solvation sheath within strong solvents,effectively addressing all three of these challenges to bolster low-temperature performance.The developed electrolyte,characterized by an enhanced concentration of contact ion pairs(CIPs)and aggregates(AGGs),facilitates the formation of an inorganic-rich interphase layer on the anode and cathode particles.This promotes de-solvation at low temperatures and stabilizes the electrode-electrolyte interphase.Full cells composed of LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM622)and graphite,when equipped with this electrolyte,showcase remarkable cycle stability and capacity retention,with 93.3% retention after 500 cycles at room temperature(RT)and 95.5%after 120 cycles at -20℃.This study validates the utility of the anion-rich solvation sheath in strong solvents as a strategy for the development of low-temperature electrolytes.
文摘The rising need for efficient and sustainable energy storage systems has led to increased interest in the use of advanced electrolytes consisting of deep eutectic solvents(DESs) and ionic liquids(ILs).These electrolytes are appealing candidates for supercapacitors,next-generation lithium-ion batteries,and different energy storage systems because of their special features including non-flammability,low volatility,lowtoxicity,good electrochemical stability,and good thermal and chemical stability.This review explores the advantages of the proposed electrolytes by examining their potential to address the critical challenges in lithium battery technology,including safety concerns,energy density limitations,and operational stability.To achieve this,a comprehensive overview of the lithium salts commonly employed in rechargeable lithium battery electrolytes is presented.Moreover,key physicochemical and functional attributes of ILs and DESs,such as electrochemical stability,ionic conductivity,nonflammability,and viscosity are also discussed with a focus on how these features impact battery performance.The integration of lithium salts with ILs and DESs in modern lithium battery technologies,including lithium-ion(Li-ion) batteries,lithium-oxygen(Li-O_(2)) batteries,and lithium-sulfur(Li-S) batteries,are further examined in the study.Various electrochemical performance metrics including cycling stability,charge/discharge profiles,retention capacity and battery's couiombic efficiency(CE) are also analyzed for the above-mentioned systems.By summarizing recent advances and challenges,this review also highlights the potential of electrolytes consisting of DESs and ILs to enhance energy density,durability,and safety in future energy storage applications.Additionally future research directions,including the molecular optimization of ILs and DESs,optimizing lithium salt compositions,and developing scalable synthesis methods to accelerate their practical implementation in next-generation energy storage applications are also explored.
基金financially supported by the Original Exploration Project of the National Natural Science Foundation of China(No.52150079)the National Natural Science Foundation of China(Nos.U22A20130,U2004215,and 51974280)+1 种基金the Natural Science Foundation of Henan Province of China(No.232300421196)the Project of Zhongyuan Critical Metals Laboratory of China(Nos.GJJSGFYQ202304,GJJSGFJQ202306,GJJSGFYQ202323,GJJSGFYQ202308,and GJJSGFYQ202307)。
文摘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.
基金financially supported by the National Natural Science Foundation of China(Nos.22473024,22073016 and 21803011)the award of Shanghai Dongfang Scholar。
文摘The chain conformation of polymers in binary solvent mixtures is a key issue in the study of functional soft matter and lies at the heart of various applications such as smart soft materials.Based on a minimal lattice model,we employ Monte Carlo(MC)simulation to systematically investigate the effects of solvent qualities on the conformation of a single homopolymer chain in binary mixed solvents.We also perform calculations using a Flory-type mean-field theory.We focus on how the introduction of a second solvent B affects the dependence of chain conformation on the quality of solvent A.We mainly examine the effects of the composition of solvent B,denoted by x,and the interactions between the two solvents.First,when x is low,the mean-square chain radius of gyration exhibits qualitatively similar behaviors to those in an individual solvent A,with a slight chain contraction when solvent A is very good.Second,in equal-molar mixtures with x=0.5,a homopolymer chain collapses when solvent A is either poor or very good,while expands at intermediate qualities.Lastly,at large x,a chain undergoes a coil-to-globule transition with the increasing quality of solvent A when solvent B is good,but mainly adopts the collapsed conformation when solvent B is poor.Our findings not only improve our understanding on the chain conformation in binary solvent mixtures,but also provide valuable guidance on the rational design of stimuli-responsive polymeric materials.
基金financially supported by the Natural Science Foundation of Shanxi Province (20210302123167)National Key Research and Development Program (2022YFC3902505)。
文摘This study explores green and low-viscosity deep eutectic solvents(DESs) for the efficient extraction of quinoline(QUI) from wash oil.The hydrogen bond donors and acceptors constituting DESs were initially screened based on thermodynamic properties predicted by the conductor-like screening model for real solvents(COSMO-RS),followed by further selection considering the viscosity and cost of the formed DESs.Phase equilibrium experiments showed that the DES composed of triethylmethylammonium chloride and formic acid exhibited the best extraction performance among the selected candidates.Key extraction parameters were optimized experimentally,achieving a maximum QUI extraction efficiency of 97.18% under mild conditions.Molecular dynamics simulations revealed that the interactions between quaternary ammonium cations and QUI play a crucial role in the extraction mechanism.This study provides insights into the use of DESs for QUI extraction and demonstrates their potential for application to other coal tar derivatives.
基金financially supported by National Natural Science Foundation of China(No.22174129)the Natural Science Foundation of Zhejiang Province(No.LZY21E030001)the Xin-Miao Talents Program of Zhejiang Province(No.2024R403B064)。
文摘Green extraction of bioactive components from natural sources has been a hot topic in the field of chemistry and biology.As a kind of green solvents,deep eutectic solvents(DESs)have unique advantages in the extraction of bioactive substances.In recent years,as a new subgroup of DESs,the switchable deep eutectic solvents(SDESs)can realize reversible phase switching between hydrophobic and hydrophilic by external driving forces(CO_(2)/p H/temperature),allowing for the extraction of different polar components while avoiding the problem of difficult recovery of DESs.The application of SDESs reduces the consumption of large amounts of organic solvents during the extraction process,thereby promoting sustainability.In the meanwhile,it presents an advantage over traditional extraction methods in preserving product activity.Based on the recent researches on SDESs,this work summarized the composition,driving factors,and conversion mechanism of SDESs.The applications of SDESs in the extraction of natural products were primarily highlighted to provide a reference for future research.
基金supported by the National Natural Science Foundation of China(Nos.81872823,82073782,and 82241002)the Key R&D Plan of Ganjiang New District of Jiangxi(No.2023010).
文摘Candida albicans is one of the most common pathogens causing invasive fungal infections,with a mortality rate of up to 20%-50%.Amphotericin B(AmB),a biopharmaceutics classification system(BCS)IV drug,significantly inhibits Candida albicans.AmB is primarily administered via oral and intravenous infusion,but severe infusion adverse effects,nephrotoxicity,and potential hepatotoxicity limit its clinical application.Deep eutectic solvents(DESs),with excellent solubilization ability and skin permeability,are attractive for transdermal delivery.Herein,we used DESs to deliver AmB for antifungal therapy transdermally.We first prepared and characterized DESs with different stoichiometric ratios of choline(Ch)and geranate(Ge).DESs increased the solubility of AmB by a thousand-fold.In vitro and in vivo,skin permeation studies indicated that DES_(1:2)(Ch and Ge in 1:2 ratio)had the most outstanding penetration and delivered fluorescence dye to the dermis layer.Then,DES_(1:2)-AmB was prepared and in vitro antifungal tests demonstrated that DES_(1:2)-AmB had superior antifungal effects compared to AmB and DES_(1:2).Furthermore,DES_(1:2)-AmB was skin-irritating and biocompatible.In conclusion,DES-AmB provides a new and effective therapeutic solution for fungal infections.
基金supported by the National Key Research and Development Program of China(2022YFB3504702)support from Horizon-EIC,Pathfinder challenges(101070976)+3 种基金support from the National Natural Science Foundation of China(22278402,22478389)the Key Research and Development Program of Henan Province(231111241800)State Key Laboratory of Mesoscience and Engineering(MESO-23-A08)the Frontier Basic Research Projects of Institute of Process Engineering,CAS(QYJC-2023-03).
文摘Ionic liquids (ILs) and deep eutectic solvents (DESs) as green solvents have attracted dramatic attention recently due to their highly tunable properties. However, traditional experimental screening methods are inefficient and resource-intensive. The article provides a comprehensive overview of various ML algorithms, including artificial neural network (ANN), support vector machine (SVM), random forest (RF), and gradient boosting trees (GBT), etc., which have demonstrated exceptional performance in handling complex and high-dimensional data. Furthermore, the integration of ML with quantum chemical calculations and conductor-like screening model-real solvent (COSMO-RS) has significantly enhanced predictive accuracy, enabling the rapid screening and design of novel solvents. Besides, recent ML applications in the prediction and design of ILs and DESs focused on solubility, melting point, electrical conductivity, and other physicochemical properties become more and more. This paper emphasizes the potential of ML in solvent design, overviewing an efficient approach to accelerate the development of sustainable and high-performance materials, providing guidance for their widespread application in a variety of industrial processes.
基金financially supported from the National Natural Science Foundation of China(Nos.52274291,52204305)Beijing Institute of Technology Research Fund Program for Young Scholars,China(No.1740011182102).
文摘The development of low-energy consumption and environmentally friendly electrodeposition of metal/alloy films or coatings is presently one of the primary topics for the research community.For this purpose,deep eutectic solvents(DESs)are valued as electrolytes for their advantages of low operating temperature and wide electrochemical windows.At present,there is large amount of literature on this emerging field,but there are no specialized reviews of these studies.Here,after a brief introduction of DESs’concept and history,we comprehensively reviewed the lastest progress on the metal/alloy electrodeposition in DESs.Additionally,we discussed the key influence factors of the electrodeposition process and analyzed the corresponding mechanisms.Based on these,we emphasized the importance of the establishment of predictive models for dealing with the challenges in large-scale applications.
基金supported by the Scientific Research and Technology Development Projects of PetroChina(2023ZZ22-02)the Local Efficient Reform and Development Funds for Personnel Training Projectsthe China Scholarship Council(CSC)via a Ph.D.Scholarship(No.202008510128).
文摘Recently, deep eutectic solvents (DES) have received great attention in assisting water flooding and surfactant flooding to improve oil recovery because they can reduce the interfacial tension (IFT) between oil and water, inhibit surfactant adsorption, and change the wettability of rock. However, the effects of DES on the wettability of rock surface have not been thoroughly investigated in the reported studies. In this study, the effects of various DES samples on the wettability of sandstone samples are investigated using the Amott wettability measurement method. Three DES samples and several DES solutions and DES-surfactant solutions are firstly synthesized. Then, the wettability of the sandstone samples is measured using pure saline water, DES solutions, and DES-surfactant solutions, respectively. The effects of the DES samples on the wettability of the sandstone samples are investigated by comparing the measured wettability parameters, including oil displacement ratio (I_(o)), water displacement ratio (I_(w)), and wettability index (I_(A)). The Berea rock sample used in this study is weakly hydrophilic with I_(o), I_(w), and I_(A) of 0.318, 0.032, and 0.286, respectively. Being processed by the prepared DES samples, the wettability of the Berea sandstone samples is altered to hydrophilic (0.7 > I_(A) > 0.3) by increasing I_(w) but lowering Io. Similarly, DES-surfactant solutions can also modify the wettability of the Berea sandstone samples from weakly hydrophilic to hydrophilic. However, some DES-surfactant solutions can not only increase I_(w) but also increase I_(o), suggesting that the lipophilicity of those sandstone samples will be improved by the DES-surfactant solutions. In addition, micromodel flooding tests confirm the promising performance of a DES-surfactant solution in improving oil recovery and altering wettability. Moreover, the possible mechanisms of DES and DES-surfactant solutions in altering the wettability of the Berea sandstone samples are proposed. DES samples may improve the hydrophilicity by forming hydrogen bonds between rock surface and water molecules. For DES-surfactant solutions, surfactant micelles can capture oil molecules to improve the lipophilicity of those sandstone samples.
基金supported by Research Project of Petro-China Southwest Oil&Gas Field Company,China(No.2024D106-03-02).
文摘H_(2)S in natural gas and other industrial gas is seriously harmful to human health,environmental protection and the downstream industries.Efficient purification of H_(2)S containing gas is the basic process in the chemical industry.Benefiting from multiple advantages,deep eutectic solvents(DES)can be used as tailor-made green solvents,and have been booming in the fields of harmful gas removal and fuel oil desulfurization.Furthermore,significant scientific research of DES in desulfurization and purification of natural gas has accelerated the process of its practical application.This paper systematically summarizes and analyzes the removal mechanism,impact factors and challenges of DES as emerging green solvent in H_(2)S absorption and conversion.Strategies on H_(2)S removal by DES generally fall into two categories:physical absorption and chemical conversion.Although the chemical conversion of H_(2)S by DES has been less studied compared with the physical absorption,it presents great application potential.At present,the research on H_(2)S removal by DES is still in the initial stage.Therefore,it is necessary to further study the mechanism of H_(2)S removal and construct the relationship between structural properties and desulfurization performance of DES,thereby to solve the issues of sulfur blockage and low quality of sulfur paste which is suffered by conventional liquid redox desulfurization solvent system.Additionally,the methods for efficient solvent regeneration and recycling remain to be explored out to promote the practical application of iron-based DES in the field of gas desulfurization.
基金financially supported by National Natural Science Foundation of China(Nos.22101204 and 22271220)the project grant from the Innovation and Strengthening Project of Guangdong Pharmaceutical University-Special Project of the Guangdong Education Commission(No.2020KZDZX1128)+1 种基金the Research Projects of the Chinese Medicine Council of Guangdong Province(No.20231209)the Key Laboratory of Tropical Medicinal Resource Chemistry of the Ministry of Education at Hainan Normal University(No.RDZH2023001)。
文摘Reaction crystallization method is a common cocrystal synthesis approach attributed to the advantage of avoiding individual crystallization of insoluble components,but faces the defects of soluble components precipitated due to organic solvent volatilization and the formation of unwanted solvates.Our group recently proposed a slurry method based on deep eutectic solvents(DESs)for cocrystal synthesis,which is green,safe and can avoid solvate formation.However,some reactions only produce insoluble raw materials rather than cocrystals due to insufficient activity of the soluble cocrystal co-formers in DESs.Herein,combining the dual benefits of the two methods,a novel reaction crystallization method based on DESs was proposed and employed for cocrystal synthesis of nicotinamide,carbamazepine and theophylline,which can prevent individual crystallization,unwanted solvate formation,and soluble component precipitation,providing a promising alternative for green and efficient synthesis of cocrystals.
基金supported by the Major Research Plan of the National Natural Science Foundation of China(92372104)Guangdong Basic and Applied Basic Research Foundation(2022A1515110016)+3 种基金the Recruitment Program of Guangdong(2016ZT06C322)R&D Program of Guangzhou(2023A04J1364)Fundamental Research Funds for the Central Universities(2024ZYGXZR043)TCL Science and Technology Innovation Fund。
文摘Electrolyte engineering with fluoroethers as solvents offers promising potential for high-performance lithium metal batteries.Despite recent progresses achieved in designing and synthesizing novel fluoroether solvents,a systematic understanding of how fluorination patterns impact electrolyte performance is still lacking.We investigate the effects of fluorination patterns on properties of electrolytes using fluorinated 1,2-diethoxyethane(FDEE)as single solvents.By employing quantum calculations,molecular dynamics simulations,and interpretable machine learning,we establish significant correlations between fluorination patterns and electrolyte properties.Higher fluorination levels enhance FDEE stability but decrease conductivity.The symmetry of fluorination sites is critical for stability and viscosity,while exerting minimal influence on ionic conductivity.FDEEs with highly symmetric fluorination sites exhibit favorable viscosity,stability,and overall electrolyte performance.Conductivity primarily depends on lithium-anion dissociation or association.These findings provide design principles for rational fluoroether electrolyte design,emphasizing the trade-offs between stability,viscosity,and conductivity.Our work underscores the significance of considering fluorination patterns and molecular symmetry in the development of fluoroether-based electrolytes for advanced lithium batteries.
基金supported by the National Natural Science Foundation of China(22008033)the Major Program of Qingyuan Innovation Laboratory.
文摘Efficient recognition and selective capture of NH_(3)is not only beneficial for increasing the productivity of the synthetic NH_(3)industry but also for reducing air pollution.For this purpose,a group of deep eutectic solvents(DESs)consisting of glycolic acid(GA)and phenol(PhOH)with low viscosities and multiple active sites was rationally designed in this work.Experimental results show that the GA^(+)PhOH DESs display extremely fast NH_(3)absorption rates(within 51 s for equilibrium)and high NH_(3)solubility.At 313.2 K,the NH_(3)absorption capacities of GA^(+)PhOH(1:1)reach 6.75 mol/kg(at 10.7 kPa)and 14.72 mol/kg(at 201.0 kPa).The NH_(3)solubility of GA^(+)PhOH DESs at low pressures were minimally changed after more than 100 days of air exposure.In addition,the NH_(3)solubility of GA^(+)PhOH DESs remain highly stable in 10 consecutive absorption-desorption cycles.More importantly,NH_(3)can be selectively captured by GA^(+)PhOH DESs from NH_(3)/CO_(2)/N_(2)and NH_(3)/N_(2)/H_(2)mixtures.1H-NMR,Fourier transform infrared and theoretical calculations were performed to reveal the intrinsic mechanism for the efficient recognition of NH_(3)by GA^(+)PhOH DESs.
基金Support from the Australian Research Council (project ID:LP140100650)
文摘Replacement of volatile organic compounds （VOCs） by greener or more environmentally sustainable solvents is becoming increasingly important due to the increasing health and environmental concerns as well as economic pressures associated with VOCs. Solvents that are derived from biomass, namely bio-derived solvents, are a type of green solvent that have attracted intensive investigations in recent years because of their advantages over con- ventional VOCs, such as low toxicity, biodegradability and renewability. This review aims to summarize the use of bio-derived solvents in solvent extraction applications, with special emphasis given to utilization of biodiesels and terpenes. Compared with the conventional VOCs, the overall performance of these bio-derived solvents is comparable in terms of extraction yields and selectivity for natural product extraction and no difference was found for metal extraction. To date most researchers have focused on laboratory scale thermodynamics studies. Future work is required to develop and test new bio-derived solvents and understand the kinetic performance as well as solvent extraction nilnt nlant studies.
基金financially supported by the National Natural Science Foundation of China(No.22174129)the Natural Science Foundation of Zhejiang Province(No.LZY21E030001)。
文摘Deep eutectic solvents(DESs)have drawn considerable attention as a new type of green solvent since they were reported.Subsequent studies have shown that DESs have the potential to be used as“designable”solvents,which means that the precursors of DESs with different structures and properties can be screened to customize DESs for specific functions.Researchers have found that during the sample preparation process involving DESs,the specific properties of some“smart”DESs can be switched by directing external driving forces,leading to a reversible phase transition of the target solution.These"smart"DESs are called switchable deep eutectic solvents(SDESs).The advent of SDES simplifies the sample pretreatment steps,reduces the use of organic solvents,and makes solvents easy to recycle,which matches the concept of green and sustainable chemistry.Compared with the number of previous experimental studies,the reviews and summaries on SDESs are rare.Therefore,this review made a summary of the concept and research progress of SDESs based on some related works in the past decade,including composition and type,characterization,switching mechanism,etc.It is expected to provide a certain reference and guidance for the subsequent in-depth research of SDESs in the analytical sample pretreatment.
基金supported by the National Natural Science Foundation of China(21773307)
文摘Biomass is renewable, abundant, cheap, biocompatible, and biodegradable materials and has been used to produce chemicals, materials,energy, and fuels. However, most of the biomass, especially most of the biomass polymers are not soluble in common solvents, which hinders their pretreatment and conversion. Deep eutectic solvents(DESs) are environmental-friendly, cheap, and highly tunable, with high solubility,which renders them potential applications in biomass pretreatment and conversion. They could be used as solvents or catalysts and so on. This paper intends to review the application of DESs for the pretreatment of biomass and conversion of biomass to value-added products. We focus on the following topics related to biomass and DESs:(1) DESs for the pretreatment of biomass;(2) DESs for the dissolution and separation of biomass or extraction of chemicals from biomass;(3) DESs for biomass conversion;(4) Drawbacks, and recyclability of DESs for pretreatment and conversion of biomass.
基金supported by the National Natural Science Foundation of China(21676230,21373177)~~
文摘Despite the significance of hydrogen bonding in deep eutectic solvents（DESs） for desulfurization processes, little is understood about the relationship between the DES composition, hydrogen-bonding strength, and oxidative desulfurization activity. In this study, a new family of caprolactam-based acidic DESs was prepared with different molar ratios of caprolactam and oxalic acid. The prepared DESs were characterized by differential scanning calorimetry, Fourier transform infrared spectroscopy, 1 H nuclear magnetic resonance, and thermogravimetric analyses. These DESs were employed for oxidative desulfurization reactions and the desulfurization efficiency was found to vary regularly with the DES composition. The factors influencing the removal of dibenzothiophene were systematically investigated and the desulfurization efficiency of the caprolactam-based acidic DESs reached as high as 98% under optimal conditions. The removal of different sulfur compounds followed the order： dibenzothiophene 4,6-dimethyldibenzothiophene benzothiophene. The combined experimental data and characterization results revealed that the oxidative desulfurization efficiency of the system was influenced by the hydrogen bonding interactions with the DES, which can be optimized by adjusting the DES composition. These findings regarding hydrogen bonding in DESs provide new insight for better understanding of the mechanism of diesel deep desulfurization processes.
