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
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 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
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
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
Sustainable energy is the key issue for the environment protection,human activity and economic development.Ionic liquids(ILs)and deep eutectic solvents(DESs)are dogmatically regarded as green and sustainable electroly...Sustainable energy is the key issue for the environment protection,human activity and economic development.Ionic liquids(ILs)and deep eutectic solvents(DESs)are dogmatically regarded as green and sustainable electrolytes in lithium-ion,lithium-metal(e.g.,lithium-sulphur,lithium-oxygen)and post-lithium-ion(e.g.,sodium-ion,magnesium-ion,and aluminum-ion)batteries.High electrochemical stability of ILs/DESs is one of the prerequisites for green,sustainable and safe energy;while easy electrochemical decomposition of ILs/DESs would be contradictory to the concept of green chemistry by adding the cost,releasing volatile/hazardous by-products and hindering the recyclability.However,(1)are ILs/DESs-based electrolytes really electrochemically stable when they are not used in batteries?(2)are ILs/DESs-based electrolytes really electrochemically stable in real batteries?(3)how to design ILs/DESs-based electrolytes with high electrochemical stability for batteries to achieve sustainability and green development?Up to now,there is no summary on this topic,to the best of our knowledge.Here,we review the effect of chemical structure and non-structural factors on the electrochemical stability of ILs/DESs in simulated conditions.More importantly,electrochemical stability of ILs/DESs in real lithium-ion,lithium-metal and post-lithium-ion batteries is concluded and compared.Finally,the strategies to improve the electrochemical stability of ILs/DESs in lithium-ion,lithium-metal and post-lithium-ion batteries are proposed.This review would provide a guide to design ILs/DESs with high electrochemical stability for lithium-ion,lithium-metal and postlithium-ion batteries to achieve sustainable and green energy.展开更多
Non-ionic deep eutectic solvents(DESs)are non-ionic designer solvents with various applications in catalysis,extraction,carbon capture,and pharmaceuticals.However,discovering new DES candidates is challenging due to a...Non-ionic deep eutectic solvents(DESs)are non-ionic designer solvents with various applications in catalysis,extraction,carbon capture,and pharmaceuticals.However,discovering new DES candidates is challenging due to a lack of efficient tools that accurately predict DES formation.The search for DES relies heavily on intuition or trial-and-error processes,leading to low success rates or missed opportunities.Recognizing that hydrogen bonds(HBs)play a central role in DES formation,we aim to identify HB features that distinguish DES from non-DES systems and use them to develop machine learning(ML)models to discover new DES systems.We first analyze the HB properties of 38 known DES and 111 known non-DES systems using their molecular dynamics(MD)simulation trajectories.The analysis reveals that DES systems have two unique features compared to non-DES systems:The DESs have①more imbalance between the numbers of the two intra-component HBs and②more and stronger inter-component HBs.Based on these results,we develop 30 ML models using ten algorithms and three types of HB-based descriptors.The model performance is first benchmarked using the average and minimal receiver operating characteristic(ROC)-area under the curve(AUC)values.We also analyze the importance of individual features in the models,and the results are consistent with the simulation-based statistical analysis.Finally,we validate the models using the experimental data of 34 systems.The extra trees forest model outperforms the other models in the validation,with an ROC-AUC of 0.88.Our work illustrates the importance of HBs in DES formation and shows the potential of ML in discovering new DESs.展开更多
The cyclic hydrogenation technology in a direct coal liquefaction process relies on the dissolved hydrogen of the solvent or oil participating in the hydrogenation reaction.Thus,a theoretical basis for process optimiz...The cyclic hydrogenation technology in a direct coal liquefaction process relies on the dissolved hydrogen of the solvent or oil participating in the hydrogenation reaction.Thus,a theoretical basis for process optimization and reactor design can be established by analyzing the solubility of hydrogen in liquefaction solvents.Experimental studies of hydrogen solubility in liquefaction solvents are challenging due to harsh reaction conditions and complex solvent compositions.In this study,the composition and content of liquefied solvents were analyzed.As model compounds,hexadecane,toluene,naphthalene,tetrahydronaphthalene,and phenanthrene were chosen to represent the liquefied solvents in chain alkanes and monocyclic,bicyclic,and tricyclic aromatic hydrocarbons.The solubility of hydrogen X(mol/mol)in pure solvent components and mixed solvents(alkanes and aromatics mixed in proportion to the chain alkanes+bicyclic aromatic hydrocarbons,bicyclic saturated aromatic hydrocarbons+bicyclic aromatic hydrocarbons,and bicyclic aromatic hydrocarbons+compounds containing het-eroatoms composed of mixed components)are determined using Aspen simulation at temperature and pressure conditions of 373–523 K and 2–10 MPa.The results demonstrated that at high temperatures and pressures,the solubility of hydrogen in the solvent increases with the increase in temperature and pressure,with the pressure having a greater impact.Further-more,the results revealed that hydrogen is more soluble in straight-chain alkanes than in other solvents,and the solubility of eicosanoids reaches a maximum of 0.296.The hydrogen solubility in aromatic ring compounds decreased gradually with an increase in the aromatic ring number.The influence of chain alkanes on the solubility of hydrogen predominates in a mixture of solvents with different mixing ratios of chain alkanes and aromatic hydrocarbons.The solubility of hydrogen in mixed aromatic solvents is less than that in the corresponding single solvents.Hydrogen is less soluble in solvent compounds containing heteroatoms than in compounds without heteroatoms.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
To improve the adsorption and catalytic performance of heterogeneous Fenton-like catalysts for oil wastes,amino acids were used to modify nanoscale zero-valent iron(AA@Fe^(0)),which were applied in the Fenton-like deg...To improve the adsorption and catalytic performance of heterogeneous Fenton-like catalysts for oil wastes,amino acids were used to modify nanoscale zero-valent iron(AA@Fe^(0)),which were applied in the Fenton-like degradation of organic solvents(tributyl phosphate and n-dodecane,named TBP and DD).Twelve amino acids,i.e.,glycine(Gly),alanine(Ala),leucine(Leu),proline(Pro),phenylalanine(Phe),methionine(Met),cysteine(Cys),asparagine(Asn),serine(Ser),glutamic acid(Glu),lysine(Lys)and arginine(Arg),were selected and calculated by density functional theory(DFT).The optimized structure,charge distribution,the highest occupied molecular orbital(HOMO),the lowest unoccupied molecular orbital(LUMO),interaction region indicator(IRI)isosurface map and adsorption energy of AA@Fe^(0),AA@Fe^(0)-TBP and AA@Fe^(0)-DD were studied,which indicated that Fe is more likely to approach and charge transfer with-COO and-NH_(3) on theα-carbon of amino acids.There is strong attraction between Fe and–COO,and Van der Waals force between Fe and-NH_(3),respectively.In the interaction of AA@Fe^(0)with TBP and DD,Van der Waal force plays an important role.AA@Fe^(0)was synthesized in laboratory and characterized to investigate physicochemical properties.In Fenton-like degradation of organic solvents,the change of COD in water phase during the degradation process as well as the volume of the organic phase after the reaction were investigated.The results of calculations combined with experiments showed that Ser-modified Fe^(0)performed the best in these amino acids,with 98%removal of organic solvents.A possible catalytic mechanism was proposed in which amino acids acted a linking role between Fe and organic solvents,activating H_(2)O_(2)to generate hydroxyl radicals for the degradation of organic solvents.展开更多
As a new concept having emerged in last few years,the“deep eutectic solvents”(DESs)effect integrated into the imprinting technology inevitably exposes design limitations of stimuli-responsive molecularly imprinted p...As a new concept having emerged in last few years,the“deep eutectic solvents”(DESs)effect integrated into the imprinting technology inevitably exposes design limitations of stimuli-responsive molecularly imprinted polymers(MIPs),as well as inadequate analysis of the adsorption performance of MIPs.Herein,a simple yet defined N-isopropylacrylamide/(3-acrylamidopropyl)trimethylammonium chloride(NIPAM/APTMAC)binary DESs system was proposed to prepare intelligent MIPs with thermo-sensitivity.Accordingly,magnetic and thermo-responsive MIPs based on functional monomers-derived DESs(TMDESs-MIPs1)were synthesized,revealing DESs effect-regulated affinity/kinetics for the enhanced adsorption capability,eco-friendly thermo-regulated elution for high release efficiency,and simple magnetic separation,along with superior selectivity to rhein(RH)and good regeneration ability.TM-DESs-MIPs1 were utilized to extract RH from Cassiae semen samples coupled with high performance liquid chromatography(HPLC),yielding satisfactory recoveries(79.47%−110.82%)and low limits of detection(LOD)(16.67μg/L).Another two kinds of MIPs adopting the thermo-responsive moiety-derived DESs effect strategy further demonstrated great applicability of such intelligent MIPs for analyses of complicated samples.展开更多
Rechargeable magnesium(Mg)-metal batteries have brought great expect to overcome the safety and energy density concerns of typical lithium-ion batteries.However,interracial passivation of the Mgmetal anode impairs the...Rechargeable magnesium(Mg)-metal batteries have brought great expect to overcome the safety and energy density concerns of typical lithium-ion batteries.However,interracial passivation of the Mgmetal anode impairs the reversible Mg plating/stripping chemistries,resulting in low Coulombic efficiency and large overpotential.In this work,a facile isobutylamine(IBA)-assisted activation strategy has been proposed and the fundamental mechanism has been unveiled in a specific way of evolving active species and forming MgH_(2)-based solid-electrolyte interphase.After introducing IBA into a typical electrolyte of magnesium bis(trifluoromethanesulfo nyl) imide(Mg(TFSI)_(2)) in diglyme(G2) solvents,electrolyte species of [Mg^(2+)(IBA)5]^(2+) and protonated amine-based cations of [(IBA)H]^(+) have been detected by nuclear magnetic resonance and mass spectra.This not only indicates direct solvation of IBA toward Mg^(2+)but also suggests its ionization,which is central to mitigating the decomposition of G2 and TFSI anions by forming neutrally charged [(IBAH^(+))(TFSI^(-))]~0 and other complex ions.A series of experiments,including cryogenic-electron microscopy,D_(2)O titration-mass spectra,and time of flight secondary ion mass spectrometry results,reveal a thin,non-passivated,and MgH_(2)-containing interphase on the Mg-metal anode.Besides,uniform and dendrite-free Mg electrodeposits have been revealed in composite electrolytes.Benefiting from the activation effects of IBA,the composite electrolyte displays superior electrochemical performance(overpotential is approximately 0.16 V versus 2.00 V for conventional electrolyte;Coulombic efficiency is above 90% versus <10% for conventional electrolyte).This work offers a fresh direction to advanced electrolyte design for next-generation rechargeable batteries.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℃ to form H_(3)PO_(4)/nZnCl_(2) (n = 0.1, 0.25, 0.5, 0.75, 1). The DESs were ch...A series of Lewis-acid deep eutectic solvents (DESs) were synthesized by stirring phosphoric acid and zincchloride as raw materials at 80℃ to form H_(3)PO_(4)/nZnCl_(2) (n = 0.1, 0.25, 0.5, 0.75, 1). The DESs were characterized byFourier transform infrared spectrophotometry (FT-IR), thermogravimetry/differential thermogravimetry (TG/DTG), andelectron spray ionization mass spectrometry (ESI-MS). The DESs were used as both extractants and catalysts to removedibenzothiophene from fuels via oxidative desulfurization (ODS). Experiments were performed to investigated the influenceof factors such as composition of DES, temperature, oxidant dosage (molar ratio of O:S), DES dosage (volume ratio ofDES:oil), and number of cycles on desulfurization rate. The results indicated that the removal rate of dibenzothiophene (DBT)was affected by the Lewis acidic DESs, with that of H_(3)PO_(4)/0.25∙ZnCl_(2) reaching 96.4% under optimal conditions (Voil=5 mL,VDES=1 mL, an oxidant dosage of 6, T=50 ℃). After six cycles, the desulfurization rate of H_(3)PO_(4)/0.25∙ZnCl_(2) remained above94.1%. The apparent activation energy of dibenzothiophene (DBT) removal reaction was determined by a pseudo-first orderkinetic equation according to the Arrhenius equation to be 32.34 kJ/mol, as estimated. A reaction mechanism is proposedbased on the experimental data and characterization results.展开更多
N/B co-doped porous carbon materials(NBPCs)are regarded as an ideal cathode material for Zn-ion hybrid supercapacitors(ZHSCs).As a capacitive cathode material,the improvement of specific surface area(SSA)and pore stru...N/B co-doped porous carbon materials(NBPCs)are regarded as an ideal cathode material for Zn-ion hybrid supercapacitors(ZHSCs).As a capacitive cathode material,the improvement of specific surface area(SSA)and pore structure can efficiently enhance the capacity and rate capability of NBPCs.However,the B atom doping progress will patch up the defect and pore of NBPCs,thereby impeding the further expansion of the SSA area and porous structure.This paper designs a new route for high-efficiency fabrication of NBPCs with high SSA and rich pore structure,employing biomass waste as the carbon source and a novel deep eutectic solvent(DES)as the activation agent.The obtained NBPCs process superior SSA(2270 m^(2)g^(-1))and abundant pore structure with rich B,N-doping level.Notably,an interesting occupied effect of doped B atoms on the N-doped carbon network can be identified,which optimizes the proportion of N-contained surface functional groups,leading to the enhancement of conductivity and capacity in NBPCs.Together with the large SSA,high B,N-doping level,an appropriate proportion of N-contained surface groups,and hierarchical porous structure,the NBPC-3 sample exhibits excellent electrochemical performance as cathode materials for ZHSCs,with an energy density of 139.46 W h kg^(-1).展开更多
In this study we used the deep eutectic solvents (ionic liquids) to investigate the reaction between copper (II) with ethylene diamine (en). Two of the existing methods for analyzing spectrophotometric measurements ha...In this study we used the deep eutectic solvents (ionic liquids) to investigate the reaction between copper (II) with ethylene diamine (en). Two of the existing methods for analyzing spectrophotometric measurements have been applied for establishing, the stoichiometry and whenever possible, the stability constants of the chelates formed. The method of continuous variations was necessary to determine first whether, the metal ion and the ligand ethylene diamine form one or more than one chelate, when more than one chelate formed, the results obtained depend on the wavelength and for meaningful conclusions the wavelengths were carefully selected. The empirical formulae of the chelates were further substantiated by the molar ratio method. The effect of time and temperature on the formation and stability of these chelates in solution is also studied. The stability constants, K1 and K2 for the copper (II) chelates were calculated, though reliable, and are comparable to literature values.展开更多
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.
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.
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supported by National Natural Science Foundation of China(22103030,22073112)Youth Topnotch Talent Program of Hebei Institution of Higher Learning(BJ2021057)for financial support.
文摘Sustainable energy is the key issue for the environment protection,human activity and economic development.Ionic liquids(ILs)and deep eutectic solvents(DESs)are dogmatically regarded as green and sustainable electrolytes in lithium-ion,lithium-metal(e.g.,lithium-sulphur,lithium-oxygen)and post-lithium-ion(e.g.,sodium-ion,magnesium-ion,and aluminum-ion)batteries.High electrochemical stability of ILs/DESs is one of the prerequisites for green,sustainable and safe energy;while easy electrochemical decomposition of ILs/DESs would be contradictory to the concept of green chemistry by adding the cost,releasing volatile/hazardous by-products and hindering the recyclability.However,(1)are ILs/DESs-based electrolytes really electrochemically stable when they are not used in batteries?(2)are ILs/DESs-based electrolytes really electrochemically stable in real batteries?(3)how to design ILs/DESs-based electrolytes with high electrochemical stability for batteries to achieve sustainability and green development?Up to now,there is no summary on this topic,to the best of our knowledge.Here,we review the effect of chemical structure and non-structural factors on the electrochemical stability of ILs/DESs in simulated conditions.More importantly,electrochemical stability of ILs/DESs in real lithium-ion,lithium-metal and post-lithium-ion batteries is concluded and compared.Finally,the strategies to improve the electrochemical stability of ILs/DESs in lithium-ion,lithium-metal and post-lithium-ion batteries are proposed.This review would provide a guide to design ILs/DESs with high electrochemical stability for lithium-ion,lithium-metal and postlithium-ion batteries to achieve sustainable and green energy.
基金supported by Ignite Research Collaborations(IRC),Startup funds,and the UK Artificial Intelligence(AI)in Medicine Research Alliance Pilot(NCATS UL1TR001998 and NCI P30 CA177558)。
文摘Non-ionic deep eutectic solvents(DESs)are non-ionic designer solvents with various applications in catalysis,extraction,carbon capture,and pharmaceuticals.However,discovering new DES candidates is challenging due to a lack of efficient tools that accurately predict DES formation.The search for DES relies heavily on intuition or trial-and-error processes,leading to low success rates or missed opportunities.Recognizing that hydrogen bonds(HBs)play a central role in DES formation,we aim to identify HB features that distinguish DES from non-DES systems and use them to develop machine learning(ML)models to discover new DES systems.We first analyze the HB properties of 38 known DES and 111 known non-DES systems using their molecular dynamics(MD)simulation trajectories.The analysis reveals that DES systems have two unique features compared to non-DES systems:The DESs have①more imbalance between the numbers of the two intra-component HBs and②more and stronger inter-component HBs.Based on these results,we develop 30 ML models using ten algorithms and three types of HB-based descriptors.The model performance is first benchmarked using the average and minimal receiver operating characteristic(ROC)-area under the curve(AUC)values.We also analyze the importance of individual features in the models,and the results are consistent with the simulation-based statistical analysis.Finally,we validate the models using the experimental data of 34 systems.The extra trees forest model outperforms the other models in the validation,with an ROC-AUC of 0.88.Our work illustrates the importance of HBs in DES formation and shows the potential of ML in discovering new DESs.
基金the financial support from the National Key Research and Development Program of China(2022YFB4101302-01)the National Natural Science Foundation of China(22178243)the science and technology innovation project of China Shenhua Coal to Liquid and Chemical Company Limited(MZYHG-22–02).
文摘The cyclic hydrogenation technology in a direct coal liquefaction process relies on the dissolved hydrogen of the solvent or oil participating in the hydrogenation reaction.Thus,a theoretical basis for process optimization and reactor design can be established by analyzing the solubility of hydrogen in liquefaction solvents.Experimental studies of hydrogen solubility in liquefaction solvents are challenging due to harsh reaction conditions and complex solvent compositions.In this study,the composition and content of liquefied solvents were analyzed.As model compounds,hexadecane,toluene,naphthalene,tetrahydronaphthalene,and phenanthrene were chosen to represent the liquefied solvents in chain alkanes and monocyclic,bicyclic,and tricyclic aromatic hydrocarbons.The solubility of hydrogen X(mol/mol)in pure solvent components and mixed solvents(alkanes and aromatics mixed in proportion to the chain alkanes+bicyclic aromatic hydrocarbons,bicyclic saturated aromatic hydrocarbons+bicyclic aromatic hydrocarbons,and bicyclic aromatic hydrocarbons+compounds containing het-eroatoms composed of mixed components)are determined using Aspen simulation at temperature and pressure conditions of 373–523 K and 2–10 MPa.The results demonstrated that at high temperatures and pressures,the solubility of hydrogen in the solvent increases with the increase in temperature and pressure,with the pressure having a greater impact.Further-more,the results revealed that hydrogen is more soluble in straight-chain alkanes than in other solvents,and the solubility of eicosanoids reaches a maximum of 0.296.The hydrogen solubility in aromatic ring compounds decreased gradually with an increase in the aromatic ring number.The influence of chain alkanes on the solubility of hydrogen predominates in a mixture of solvents with different mixing ratios of chain alkanes and aromatic hydrocarbons.The solubility of hydrogen in mixed aromatic solvents is less than that in the corresponding single solvents.Hydrogen is less soluble in solvent compounds containing heteroatoms than in compounds without heteroatoms.
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supported by the National Natural Science Foundation of China (No.22176067)。
文摘To improve the adsorption and catalytic performance of heterogeneous Fenton-like catalysts for oil wastes,amino acids were used to modify nanoscale zero-valent iron(AA@Fe^(0)),which were applied in the Fenton-like degradation of organic solvents(tributyl phosphate and n-dodecane,named TBP and DD).Twelve amino acids,i.e.,glycine(Gly),alanine(Ala),leucine(Leu),proline(Pro),phenylalanine(Phe),methionine(Met),cysteine(Cys),asparagine(Asn),serine(Ser),glutamic acid(Glu),lysine(Lys)and arginine(Arg),were selected and calculated by density functional theory(DFT).The optimized structure,charge distribution,the highest occupied molecular orbital(HOMO),the lowest unoccupied molecular orbital(LUMO),interaction region indicator(IRI)isosurface map and adsorption energy of AA@Fe^(0),AA@Fe^(0)-TBP and AA@Fe^(0)-DD were studied,which indicated that Fe is more likely to approach and charge transfer with-COO and-NH_(3) on theα-carbon of amino acids.There is strong attraction between Fe and–COO,and Van der Waals force between Fe and-NH_(3),respectively.In the interaction of AA@Fe^(0)with TBP and DD,Van der Waal force plays an important role.AA@Fe^(0)was synthesized in laboratory and characterized to investigate physicochemical properties.In Fenton-like degradation of organic solvents,the change of COD in water phase during the degradation process as well as the volume of the organic phase after the reaction were investigated.The results of calculations combined with experiments showed that Ser-modified Fe^(0)performed the best in these amino acids,with 98%removal of organic solvents.A possible catalytic mechanism was proposed in which amino acids acted a linking role between Fe and organic solvents,activating H_(2)O_(2)to generate hydroxyl radicals for the degradation of organic solvents.
基金National Key Research and Development Project(No.2019YFC1604904)National Natural Science Foundation of China(No.32101212)+1 种基金Natural Science Foundation of Jiangxi(No.20224ACB215009)Research Program of State Key Laboratory of Food Science and Technology in Nanchang University(No.SKLF-ZZB-202127).
文摘As a new concept having emerged in last few years,the“deep eutectic solvents”(DESs)effect integrated into the imprinting technology inevitably exposes design limitations of stimuli-responsive molecularly imprinted polymers(MIPs),as well as inadequate analysis of the adsorption performance of MIPs.Herein,a simple yet defined N-isopropylacrylamide/(3-acrylamidopropyl)trimethylammonium chloride(NIPAM/APTMAC)binary DESs system was proposed to prepare intelligent MIPs with thermo-sensitivity.Accordingly,magnetic and thermo-responsive MIPs based on functional monomers-derived DESs(TMDESs-MIPs1)were synthesized,revealing DESs effect-regulated affinity/kinetics for the enhanced adsorption capability,eco-friendly thermo-regulated elution for high release efficiency,and simple magnetic separation,along with superior selectivity to rhein(RH)and good regeneration ability.TM-DESs-MIPs1 were utilized to extract RH from Cassiae semen samples coupled with high performance liquid chromatography(HPLC),yielding satisfactory recoveries(79.47%−110.82%)and low limits of detection(LOD)(16.67μg/L).Another two kinds of MIPs adopting the thermo-responsive moiety-derived DESs effect strategy further demonstrated great applicability of such intelligent MIPs for analyses of complicated samples.
基金National Natural Science Foundation of China (22279068, 51972187)Natural Science Foundation of Shandong Province (ZR2021QE166)Qingdao New Energy Shandong Laboratory Open Project (QNESL OP202312)。
文摘Rechargeable magnesium(Mg)-metal batteries have brought great expect to overcome the safety and energy density concerns of typical lithium-ion batteries.However,interracial passivation of the Mgmetal anode impairs the reversible Mg plating/stripping chemistries,resulting in low Coulombic efficiency and large overpotential.In this work,a facile isobutylamine(IBA)-assisted activation strategy has been proposed and the fundamental mechanism has been unveiled in a specific way of evolving active species and forming MgH_(2)-based solid-electrolyte interphase.After introducing IBA into a typical electrolyte of magnesium bis(trifluoromethanesulfo nyl) imide(Mg(TFSI)_(2)) in diglyme(G2) solvents,electrolyte species of [Mg^(2+)(IBA)5]^(2+) and protonated amine-based cations of [(IBA)H]^(+) have been detected by nuclear magnetic resonance and mass spectra.This not only indicates direct solvation of IBA toward Mg^(2+)but also suggests its ionization,which is central to mitigating the decomposition of G2 and TFSI anions by forming neutrally charged [(IBAH^(+))(TFSI^(-))]~0 and other complex ions.A series of experiments,including cryogenic-electron microscopy,D_(2)O titration-mass spectra,and time of flight secondary ion mass spectrometry results,reveal a thin,non-passivated,and MgH_(2)-containing interphase on the Mg-metal anode.Besides,uniform and dendrite-free Mg electrodeposits have been revealed in composite electrolytes.Benefiting from the activation effects of IBA,the composite electrolyte displays superior electrochemical performance(overpotential is approximately 0.16 V versus 2.00 V for conventional electrolyte;Coulombic efficiency is above 90% versus <10% for conventional electrolyte).This work offers a fresh direction to advanced electrolyte design for next-generation rechargeable batteries.
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℃ 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supported by the National Natural Science Foundation of China Project(No.52163001)the Guizhou Minzu University Research Platform Grant(No.GZMUGCZX[2021]01)+1 种基金the Guizhou Provincial Science and Technology Program Project Grant(Nos.Qiankehe Platform Talents-CXTD[2021]005Qiankehe Platform Talents-GCC[2022]010-1).
文摘N/B co-doped porous carbon materials(NBPCs)are regarded as an ideal cathode material for Zn-ion hybrid supercapacitors(ZHSCs).As a capacitive cathode material,the improvement of specific surface area(SSA)and pore structure can efficiently enhance the capacity and rate capability of NBPCs.However,the B atom doping progress will patch up the defect and pore of NBPCs,thereby impeding the further expansion of the SSA area and porous structure.This paper designs a new route for high-efficiency fabrication of NBPCs with high SSA and rich pore structure,employing biomass waste as the carbon source and a novel deep eutectic solvent(DES)as the activation agent.The obtained NBPCs process superior SSA(2270 m^(2)g^(-1))and abundant pore structure with rich B,N-doping level.Notably,an interesting occupied effect of doped B atoms on the N-doped carbon network can be identified,which optimizes the proportion of N-contained surface functional groups,leading to the enhancement of conductivity and capacity in NBPCs.Together with the large SSA,high B,N-doping level,an appropriate proportion of N-contained surface groups,and hierarchical porous structure,the NBPC-3 sample exhibits excellent electrochemical performance as cathode materials for ZHSCs,with an energy density of 139.46 W h kg^(-1).
文摘In this study we used the deep eutectic solvents (ionic liquids) to investigate the reaction between copper (II) with ethylene diamine (en). Two of the existing methods for analyzing spectrophotometric measurements have been applied for establishing, the stoichiometry and whenever possible, the stability constants of the chelates formed. The method of continuous variations was necessary to determine first whether, the metal ion and the ligand ethylene diamine form one or more than one chelate, when more than one chelate formed, the results obtained depend on the wavelength and for meaningful conclusions the wavelengths were carefully selected. The empirical formulae of the chelates were further substantiated by the molar ratio method. The effect of time and temperature on the formation and stability of these chelates in solution is also studied. The stability constants, K1 and K2 for the copper (II) chelates were calculated, though reliable, and are comparable to literature values.
