Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However...Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However,the underlying microscopic mechanism remains ambiguous.In this work,the multiscale reaction density functional theory is applied to explore the effect of 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_(6)])solvent on the reaction of cyclopentadiene(CP)with acrolein,methyl acrylate,or acrylonitrile.By analyzing the free energy landscape during the reaction,it is found that the polarization effect has a relatively small influence,while the solvation effect makes both the activation free energy and reaction free energy decrease.In addition,the rearrangement of local solvent structure shows that the cation spatial distribution responds more evidently to the reaction than the anion,and this indicates that the cation plays a dominant role in the solvation effect and so as to affect the reaction rates and selectivity of the DA reactions.展开更多
The dramatic temperature-dependence of liquids dynamics has attracted considerable scientific interests and efforts in the past decades, but the physics of which remains elusive. In addition to temperature, some other...The dramatic temperature-dependence of liquids dynamics has attracted considerable scientific interests and efforts in the past decades, but the physics of which remains elusive. In addition to temperature, some other parameters, such as pressure, loading and size, can also tune the liquid dynamics and induce glass transition, which makes the situation more complicated. Here, we performed molecular dynamics simulations for Ni_(50)Zr_(50) bulk liquid and nanodroplet to study the dynamics evolution in the complex multivariate phase space, especially along the isotherm with the change of pressure or droplet size. It is found that the short-time Debye–Waller factor universally determines the long-time relaxation dynamics no matter how the temperature, pressure or size changes. The basic correlation even holds at the local atomic scale. This finding provides general understanding of the microscopic mechanism of dynamic arrest and dynamic heterogeneity.展开更多
The separation of aromatics from aliphatics is essential for achieving maximum exploitation of oil resources in the petrochemical industry.In this study,a series of metal chloride-based ionic liquids were prepared and...The separation of aromatics from aliphatics is essential for achieving maximum exploitation of oil resources in the petrochemical industry.In this study,a series of metal chloride-based ionic liquids were prepared and their performances in the separation of 1,2,3,4-tetrahydronaphthalene(tetralin)/dodecane and tetralin/decalin systems were studied.Among these ionic liquids,1-ethyl-3-methylimidazolium tetrachloroferrate([EMIM][FeCl_(4)])with the highest selectivity was used as the extractant.Density functional theory calculations showed that[EMIM][FeCl_(4)]interacted more strongly with tetralin than with dodecane and decalin.Energy decomposition analysis of[EMIM][FeCl_(4)]-tetralin indicated that electrostatics and dispersion played essential roles,and induction cannot be neglected.The van der Waals forces was a main effect in[EMIM][FeCl_(4)]-tetralin by independent gradient model analysis.The tetralin distribution coefficient and selectivity were 0.8 and 110,respectively,with 10%(mol)tetralin in the initial tetralin/dodecane system,and 0.67 and 19.5,respectively,with 10%(mol)tetralin in the initial tetralin/decalin system.The selectivity increased with decreasing alkyl chain length of the extractant.The influence of the extraction temperature,extractant dosage,and initial concentrations of the system components on the separation performance were studied.Recycling experiments showed that the regenerated[EMIM][FeCl_(4)]could be used repeatedly.展开更多
With the vigorous development of the electronics industry,the consumption of lithium continues to increase,and more lithium needs to be mined to meet the development of the industry.The content of lithium in the solut...With the vigorous development of the electronics industry,the consumption of lithium continues to increase,and more lithium needs to be mined to meet the development of the industry.The content of lithium in the solution is much higher than that of minerals,but the interference of impurity ions increases the difficulty of extracting lithium ions.Therefore,we prepared an imidazole-based ionic liquid(1-butyl-3-methylImidazolium bis(trifluoromethyl sulfonyl)imide)(IL)for efficient lithium extraction from aqueous solutions by solvent extraction.Using an extraction consisting of 10%IL,85% tributyl phosphate(TBP),and 5% dichloroethane and an organic to aqueous phase ratio(O/A)of 2/1,over 64.23% of Li were extracted,and the extraction rate after five-stage extraction could reach more than 96%.The addition of ammonium ions to the solution inhibited the extraction of Ni,and the separation coefficient between lithium and nickel approached infinity,showing a very perfect separation effect.Fouriertransform infrared spectroscopy and slope methods were used to analyze the changes that occurred during extraction,revealing possible extraction mechanisms.In addition,the LiCl solution generated during the preparation of ionic liquids was mixed with the stripping solution,and the battery-grade lithium carbonate was prepared by Na_(2)CO_(3) precipitation,with a purity of 99.74%.This study provides an efficient and sustainable strategy for recovering lithium from the solution.展开更多
The transformation of CO_(2)into high value-added product is a promising pathway for utilizing CO_(2).However,the process tends to require harsh reaction conditions owing to CO_(2)chemical inertness.Designing a high e...The transformation of CO_(2)into high value-added product is a promising pathway for utilizing CO_(2).However,the process tends to require harsh reaction conditions owing to CO_(2)chemical inertness.Designing a high efficiency catalytic system with environmentally benign characteristic are important determinants.In this work,protic ionic liquids[TMG][2-OPy]were prepared via one-step neutralization between 1,1,3,3-tetramethylguanidine and 2-hydroxypyridine,applying to the domain of synthesizing quinzoline-2,4(1 H,3H)-diones from CO_(2)and 2-aminobenzontiles without any solvent or metal,achieving the yield of 97%at 90℃for 8 h under atmospheric.A series of substrates with good to acceptable yield were detected,revealing the generality and universality of the catalyst.Furthermore,the system could be facilely reused for at least six runs,retaining the yield of 94%.A preliminary kinetic equation is calculated with the activation energy of 68 kJ·mol^(-1),and a plausible reaction mechanism was put forward.This study highlights that the[TMG][2-OPy]enables to activate CO_(2)carboxylation efficiently.展开更多
Metal halide perovskite solar cells(PSCs)have shown great potential to become the next generation of photovoltaic devices due to their simple fabrication techniques,low cost,and soaring power conversion efficiency(PCE...Metal halide perovskite solar cells(PSCs)have shown great potential to become the next generation of photovoltaic devices due to their simple fabrication techniques,low cost,and soaring power conversion efficiency(PCE).However,mismatched with the quickly updated PCEs,the improvement of device stability is challenging and still remains a critical hurdle in the path to commercialization.Recently,ionic liquids(ILs)have been found to play multiple roles in obtaining efficient and stable PSCs.These ILs usually consist of large organic cations and organic or inorganic anions,which have weak electrostatic attraction and are generally liquid at around 100℃.ILs are almost non-volatile,non-flammable,with high ionic conductivity and excellent thermal and electrochemical stability.The roles of ILs in PSCs vary with their composition,that is,the types of anions and cations.In this review,we summarize the roles of anions and cations in terms of precursor solutions,additives,perovskite/charge transport layer interface engineering,and charge transport layers.This article aims to set up a structure–property-stability-performance correlations conferred by the IL in PSC and provide assistance for the anion and cation selection for improving the quality of perovskite film,optimizing interface contact,reducing defect states,and improving charge extraction and transport characteristics.Finally,the application of IL in PSCs is discussed and prospected.展开更多
Diphenyl carbonate(DPC)is one of the versatile carbonates,and is often used for the production of polycarbonates.In recent years,the catalytic synthesis of DPC has become an important topic but the development of a hi...Diphenyl carbonate(DPC)is one of the versatile carbonates,and is often used for the production of polycarbonates.In recent years,the catalytic synthesis of DPC has become an important topic but the development of a highly active metal-free catalyst is a great challenge.Herein,a series of ionic liquids-SBA-15 hybrid catalysts with different functional groups have been developed for the synthesis of DPC under solventfree condition,which are effective and clean instead of the metal-containing catalysts.It is found that in the presence of[SBA-15-IL-OH]Br catalyst,methyl phenyl carbonate(MPC)conversion of 80.5%along with 99.6%DPC selectivity is achieved,the TOF value is thrice higher than the best value reported by using transition metal-based catalysts.Moreover,the catalyst displays remarkable stability and recyclability.This work provides a new idea to design and prepare eco-friendly catalysts in a broad range of applications for the green synthesis of carbonates.展开更多
Phenol in waste water threatens human health and is difficultly to be decomposed by nature.Efficient degradation of high-loaded phenol in water under mild condition is still a great challenge.Herein,ionic liquids with...Phenol in waste water threatens human health and is difficultly to be decomposed by nature.Efficient degradation of high-loaded phenol in water under mild condition is still a great challenge.Herein,ionic liquids with tungstate anion were designed and prepared.It was found that dodecyltrimethylammonium tungstate could catalyzed degradation of phenol into gases and water thoroughly at 323 k in 8 h.Tungstate anion revealed good catalytic oxidative activity and long carbon chain group connecting with cation of ionic liquids enriched phenol around catalysts,which induced the complete degradation of phenol at mild conditions.Increasing the amounts of hydrogen peroxide benefited to the total degradation of phenol.In addition,the ionic liquid could be reused for its excellent thermal stability.Our work provided a different strategy to treat waste water containing phenol efficiently.展开更多
The hydrodynamic study of the liquid film around Taylor bubbles in slug flow has great significance for understanding parallel flow and interaction between Taylor bubbles.The prediction models for liquid film thicknes...The hydrodynamic study of the liquid film around Taylor bubbles in slug flow has great significance for understanding parallel flow and interaction between Taylor bubbles.The prediction models for liquid film thickness mainly focus on stagnant flow,and some of them remain inaccurate performance.However,in the industrial process,the slug flow essentially is co-current flow.Therefore,in this paper,the liquid film thickness is studied by theoretical analysis and experimental methods under two conditions of stagnant and co-current flow.Firstly,under the condition of stagnant flow,the present work is based on Batchelor's theory,and modifies Batchelor's liquid film thickness model,which effectively improves its prediction accuracy.Under the condition of co-current flow,the prediction model of average liquid film thickness in slug flow is established by force and motion analysis.Taylor bubble length is introduced into the model as an important parameter.Dynamic experiments were carried out in the pipe with an inner diameter of 20 mm.The liquid film thickness,Taylor bubble velocity and length were measured by distributed ultrasonic sensor and intrusive cross-correlation conductivity sensor.Comparing the predicted value of the model with the measured results,the relative error is controlled within 10%.展开更多
Metal-organic frameworks(MOFs)have attracted considerable research attention as a new type of porous material for catalytic applications.Herein,2,5-dihydroxyterephthalic acid was proposed to replace conventional terep...Metal-organic frameworks(MOFs)have attracted considerable research attention as a new type of porous material for catalytic applications.Herein,2,5-dihydroxyterephthalic acid was proposed to replace conventional terephthalic acid and reacted with chromic nitrate nonahydrate to synthesize a functional metal–organic framework(FMIL-101).This was then used to immobilize various compound ionic liquids to prepare three ionic liquids immobilized on FMIL-101 catalysts,namely,FMIL-101-[HeMIM]Cl/(ZnBr_(2))_(2),FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),and FMIL-101-[AeMIM]Br/(ZnBr_(2))_(2).After characterization by Fourier-transform infrared spectroscopy,X-ray diffraction,ultraviolet spectroscopy,thermogravimetry,specific surface area analysis,and scanning electron microscopy,the catalysts were used to mediate cycloaddition reactions between carbon dioxide(CO_(2))and propylene oxide.The effects of reaction temperature,reaction pressure,reaction time,and catalyst dosage on the catalytic performance were investigated.The results revealed that the FMIL-101-supported CIL catalysts afforded the target product propylene carbonate with good catalytic performance and thermal stability.The optimal catalyst,FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),displayed a propylene oxide conversion of 98.64%and a propylene carbonate selectivity of 96.63%at a reaction temperature of 110℃,a reaction pressure of 2.0 MPa,a catalyst dosage of 2.0%relative to propylene oxide,and a reaction time of 2.5 h.In addition,the conversion and selectivity of the catalyst decreased slightly after four cycles.Additionally,the catalyst decreased slightly in catalytic performance after being recycled four times.展开更多
Light hydrocarbons(C1–C4) are fundamental raw materials in the petroleum and chemical industry. Separation and purification of structurally similar paraffin/olefin/alkyne mixtures are important for the production of ...Light hydrocarbons(C1–C4) are fundamental raw materials in the petroleum and chemical industry. Separation and purification of structurally similar paraffin/olefin/alkyne mixtures are important for the production of highpurity or even polymer-grade light hydrocarbons. However, traditional methods such as cryogenic distillation and solvent absorption are energy-intensive and environmentally unfriendly processes. Ionic liquids(ILs) as a new alternative to organic solvents have been proposed as promising green media for light hydrocarbon separation due to their unique tunable structures and physicochemical properties resulting from the variations of the cations and anions such as low volatility, high thermal stability, large liquidus range, good miscibility with light hydrocarbons, excellent molecular recognition ability and adjustable hydrophylicity/hydrophobicity. In this review, the recent progresses on the light hydrocarbon separation using ILs are summarized, and some parameters of ILs that influence the separation performance are discussed.展开更多
Low temperature coal tar contained a large amount of phenols, aromatic hydrocarbons and alkanes;the separation of phenols from coal tar has a great significance to the deep processing of coal tar. In this work, the se...Low temperature coal tar contained a large amount of phenols, aromatic hydrocarbons and alkanes;the separation of phenols from coal tar has a great significance to the deep processing of coal tar. In this work, the separation of m-cresol from cumene and n-heptane by liquid–liquid extraction using ionic liquids(ILs) as extractants was studied. The suitable ILs were screened by conductor-like screening model for real solvents(COSMO-RS)model and the liquid–liquid phase equilibrium(LLE) experiments were to verify the accuracy of the screening results. The extraction conditions such as extraction time, extraction temperature and mass ratio of ILs to model oils were evaluated. An internal mechanism of the m-cresol extract by ILs was revealed by COSMO-RS calculation and FT-IR. The results showed that the selected ILs can extract m-cresol effectively from cumene and nheptane, 1-ethyl-3-methylimidazolium acetate(emim CH3 COO) was the best extraction solvent. A hydrogen bond between anion of ILs and phenolic hydroxyl groups was observed. M-cresol in model oils could be extracted with extraction efficiencies up to 98.85% at an emim CH3 COO: model oils mass ratio of 0.5 and 298.15 K,emim CH3 COO could be regenerated and reused for 4 cycles without obvious decreases in extraction efficiency and extractant mass.展开更多
1,5-Pentanediamine(PDA)produced by biological fermentation becomes popular,but the separation of PDA from the broth is a typical difficult problem.In this work,the performance of 200 ionic liquids(ILs),formed by combi...1,5-Pentanediamine(PDA)produced by biological fermentation becomes popular,but the separation of PDA from the broth is a typical difficult problem.In this work,the performance of 200 ionic liquids(ILs),formed by combining 25 cations and 8 anions,in the extraction of PDA from aqueous solution were evaluated using COSMO-RS model.The extraction mechanism was investigated with the help ofσ-profile and interaction energy analyses.Both the cation and anion have impacts on the extraction efficiency,where cation mainly influences the interaction of IL with PDA and anion affects the hydrophobicity of IL.The IL composed of long alkyl-chain in cation and the anion of[PF6]-or[TF2 N]-,which has theσ-profile more likely distributed in the nonpolar region but less distributed in the polar region,is favorable for extraction.The experimental liquid-liquid equilibrium demonstrated the effects of cation and anion on extraction performance,which validated the reliability of COSMO-RS model in IL screening for PDA extraction.The IL[IM-1,8][PF6]could serve as a promising extractant for the downstream separation process of the biological production of PDA.展开更多
CO_2 capture with ionic liquids(ILs) has attracted many attentions, and most works focused on absorption ability at ambient temperatures, while seldom research was concerned at elevated temperatures.This not only limi...CO_2 capture with ionic liquids(ILs) has attracted many attentions, and most works focused on absorption ability at ambient temperatures, while seldom research was concerned at elevated temperatures.This not only limits the CO_2 absorption application at elevated temperature, but also the determination of the operation condition of the CO_2 desorption generally occurring at higher temperature. This work mainly reported CO_2 solubilities in ILs at elevated temperatures and related properties were also provided. 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide([CnMIm][Tf_2N]) ILs were selected as physical absorbents for CO_2 capture in this work due to their relative higher CO_2 absorption capacities and good thermal stabilities. The long-term stability tests showed that [CnMIm][Tf_2N] is thermally stable at 393.15 K for long time. CO_2 solubilities in [CnMIm][Tf_2N] were systematically determined at temperatures from 353.15 K to 393.15 K. It demonstrated that CO_2 solubility obviously increases with the increase of pressure while slightly decreases with increase of temperature. As the length of alkyl chain on the cation increases, CO_2 solubility in ILs increases. Additionally, the thermodynamic properties including the Gibbs free energy, enthalpy, and entropy of CO_2 were also calculated.展开更多
High spatial frequency laser induced periodic surface structures(HSFLs)on silicon substrates are often developed on flat surfaces at low fluences near ablation threshold of 0.1 J/cm2,seldom on microstructures or micro...High spatial frequency laser induced periodic surface structures(HSFLs)on silicon substrates are often developed on flat surfaces at low fluences near ablation threshold of 0.1 J/cm2,seldom on microstructures or microgrooves at relatively higher fluences above 1 J/cm^2.This work aims to enrich the variety of HSFLs-containing hierarchical microstructures,by femtosecond laser(pulse duration:457 fs,wavelength:1045 nm,and repetition rate:100 kHz)in liquids(water and acetone)at laser fluence of 1.7 J/cm^2.The period of Si-HSFLs in the range of 110–200 nm is independent of the scanning speeds(0.1,0.5,1 and 2 mm/s),line intervals(5,15 and 20μm)of scanning lines and scanning directions(perpendicular or parallel to light polarization direction).It is interestingly found that besides normal HSFLs whose orientations are perpendicular to the direction of light polarization,both clockwise or anticlockwise randomly tilted HSFLs with a maximal deviation angle of 50°as compared to those of normal HSFLSs are found on the microstructures with height gradients.Raman spectra and SEM characterization jointly clarify that surface melting and nanocapillary waves play important roles in the formation of Si-HSFLs.The fact that no HSFLs are produced by laser ablation in air indicates that moderate melting facilitated with ultrafast liquid cooling is beneficial for the formation of HSFLs by LALs.On the basis of our findings and previous reports,a synergistic formation mechanism for HSFLs at high fluence was proposed and discussed,including thermal melting with the concomitance of ultrafast cooling in liquids,transformation of the molten layers into ripples and nanotips by surface plasmon polaritons(SPP)and second-harmonic generation(SHG),and modulation of Si-HSFLs direction by both nanocapillary waves and the localized electric field coming from the excited large Si particles.展开更多
In this article,an efficient,simple and environmentally friendly approach to the synthesis of diacetals（diketals） pentaerythritol using SO<sub>3</sub>H-functionalized ionic liquids（ILs） as catalysts wa...In this article,an efficient,simple and environmentally friendly approach to the synthesis of diacetals（diketals） pentaerythritol using SO<sub>3</sub>H-functionalized ionic liquids（ILs） as catalysts was reported.The ILs show high catalytic activity and reusability with good to excellent yields of the desired products.Hammett method has been used to determine the acidity order of these ionic liquids and the results are consistent with the catalytic activities observed in acetalization reaction.Maximum product yield of 93%was observed on using[PSPy][OTf]as catalyst and it can be reused at least 8 times without obvious activity loss.展开更多
The pursuit of high energy density has promoted the development of high-performance lithium metal batteries.However,it faces a serious security problem.Ionic liquids have attracted great attention due to their high io...The pursuit of high energy density has promoted the development of high-performance lithium metal batteries.However,it faces a serious security problem.Ionic liquids have attracted great attention due to their high ionic conductivity,non-flammability,and the properties of promoting the formation of stable SEI films.Deeply understanding the problems existing in lithium metal batteries and the role of ionic liquids in them is of great significance for improving the performance of lithium metal batteries.This article reviews the effects of the molecular structure of ionic liquids on ionic conductivity,Li^(+)ion transference number,electrochemical stability window,and lithium metal anode/electrolyte interface,as well as the application of ionic liquids in Li-high voltage cathode batteries,Li-O_(2) batteries and Li-S batteries.The molecular design,composition and polymerization will be the main strategies for the future development of ionic liquid-based electrolytes for high performance lithium metal battery.展开更多
A large number of surplus glycerol from the biodiesel production can be used as renewable feedstock to produce glycerol carbonate. In this paper, a series of guanidine-based ionic liquids were synthesized to catalyze ...A large number of surplus glycerol from the biodiesel production can be used as renewable feedstock to produce glycerol carbonate. In this paper, a series of guanidine-based ionic liquids were synthesized to catalyze the transesterification of glycerol and dimethyl carbonate. The tunable basicity and the anion–cation cooperative effect were responsible for the obtained results. The [TMG][TFE] showed the best activity turnover frequency(TOF)of 1754.0 h^(-1), glycerol(GL) conversion of 91.8%, glycerol carbonate(GC) selectivity of 95.5%) at 80 °C with 0.1 mol% catalyst for 30 min. The reaction mechanism of the transesterification was also proposed.展开更多
The adjustable parameters in the popular conductor-like screening model for real solvents(COSMO-RS)within the Amsterdam density functional(ADF)framework have been re-optimized to fit for the systems containing ionic l...The adjustable parameters in the popular conductor-like screening model for real solvents(COSMO-RS)within the Amsterdam density functional(ADF)framework have been re-optimized to fit for the systems containing ionic liquids(ILs).To get the optimal values of misfit energy constant a^0,hydrogen bond coefficient c_(hb)and effective contact surface area of a segment a_(eff),2283 activity coefficient data points at infinite dilution and 1433 CO_2 solubility data points exhaustively collected from references were used as training set.The average relative deviations(ARDs)of activity coefficients at infinite dilution and CO_2 solubility between experimental data and predicted values are 32.22%and17.61%,respectively,both of which are significantly lower than the original COSMO-RS versions.Predictions for other activity coefficients of solutes in ILs,solubility data of CO_2 in pure ILs and the binary mixtures of ILs at either high or low temperatures,and vapor–liquid equilibrium(VLE)for binary systems involving ILs have also been performed to demonstrate the validity of the parameterization of COSMO-RS model for ILs.The results showed that the predicted results by COSMO-RS model with the new optimized parameters are in much better agreement with experimental data than those by the original versions over a wide temperature and pressure range.The COSMO-RS model for ILs presented in this work improves the prediction accuracy of thermodynamic properties for the systems containing ILs,which is always highly desirable for general chemical engineers.展开更多
Polyamide 6 underwent an efficient depolymerization in hydrophilic ionic liquids under microwave irradiation at 300C. The depolymerization completed within 60 min. Caprolactam was readily separated by simple extractio...Polyamide 6 underwent an efficient depolymerization in hydrophilic ionic liquids under microwave irradiation at 300C. The depolymerization completed within 60 min. Caprolactam was readily separated by simple extraction procedure and the ionic liquids were recovered and reused for several times. Addition of catalytic amounts of DMAP(N,N-dimethylaminopyridine) promoted the depolymerization effectively.The present improved procedure provides a method to avoid direct distillation procedure, which consumes energy for the separation of caprolactam from ionic liquids. Although some contamination of ionic liquids was observed, the present procedure provides a new possibility for the use of ionic liquids for plastic chemical recycling from the viewpoint of development of an energy-saving methodology. Use of solubility switchable ionic liquids is also examined to explore a possibility for better separation although depolymerization did not work well.展开更多
基金supported by the National Natural Science Foundation of China(22168002,22108070,21878078)the Natural Science Foundation of Guangxi Province(2020GXNSFAA159119)+2 种基金the Dean Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology(2021Z012)the Open Fund of the State Key Laboratory of Molecular Reaction Dynamics in DICP(SKLMRD-K202106)the Young Elite Scientists Sponsorship Program by CAST(2022QNRC001)。
文摘Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However,the underlying microscopic mechanism remains ambiguous.In this work,the multiscale reaction density functional theory is applied to explore the effect of 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_(6)])solvent on the reaction of cyclopentadiene(CP)with acrolein,methyl acrylate,or acrylonitrile.By analyzing the free energy landscape during the reaction,it is found that the polarization effect has a relatively small influence,while the solvation effect makes both the activation free energy and reaction free energy decrease.In addition,the rearrangement of local solvent structure shows that the cation spatial distribution responds more evidently to the reaction than the anion,and this indicates that the cation plays a dominant role in the solvation effect and so as to affect the reaction rates and selectivity of the DA reactions.
基金Project supported by the National Natural Science Foundation of China (Grant No.52031016)。
文摘The dramatic temperature-dependence of liquids dynamics has attracted considerable scientific interests and efforts in the past decades, but the physics of which remains elusive. In addition to temperature, some other parameters, such as pressure, loading and size, can also tune the liquid dynamics and induce glass transition, which makes the situation more complicated. Here, we performed molecular dynamics simulations for Ni_(50)Zr_(50) bulk liquid and nanodroplet to study the dynamics evolution in the complex multivariate phase space, especially along the isotherm with the change of pressure or droplet size. It is found that the short-time Debye–Waller factor universally determines the long-time relaxation dynamics no matter how the temperature, pressure or size changes. The basic correlation even holds at the local atomic scale. This finding provides general understanding of the microscopic mechanism of dynamic arrest and dynamic heterogeneity.
基金supported by the National Natural Science Foundation of China(22125802,22078010).
文摘The separation of aromatics from aliphatics is essential for achieving maximum exploitation of oil resources in the petrochemical industry.In this study,a series of metal chloride-based ionic liquids were prepared and their performances in the separation of 1,2,3,4-tetrahydronaphthalene(tetralin)/dodecane and tetralin/decalin systems were studied.Among these ionic liquids,1-ethyl-3-methylimidazolium tetrachloroferrate([EMIM][FeCl_(4)])with the highest selectivity was used as the extractant.Density functional theory calculations showed that[EMIM][FeCl_(4)]interacted more strongly with tetralin than with dodecane and decalin.Energy decomposition analysis of[EMIM][FeCl_(4)]-tetralin indicated that electrostatics and dispersion played essential roles,and induction cannot be neglected.The van der Waals forces was a main effect in[EMIM][FeCl_(4)]-tetralin by independent gradient model analysis.The tetralin distribution coefficient and selectivity were 0.8 and 110,respectively,with 10%(mol)tetralin in the initial tetralin/dodecane system,and 0.67 and 19.5,respectively,with 10%(mol)tetralin in the initial tetralin/decalin system.The selectivity increased with decreasing alkyl chain length of the extractant.The influence of the extraction temperature,extractant dosage,and initial concentrations of the system components on the separation performance were studied.Recycling experiments showed that the regenerated[EMIM][FeCl_(4)]could be used repeatedly.
基金supported by the National Natural Science Foundation of China(22008161)Sichuan Science and Technology Program(2022YFQ0037)。
文摘With the vigorous development of the electronics industry,the consumption of lithium continues to increase,and more lithium needs to be mined to meet the development of the industry.The content of lithium in the solution is much higher than that of minerals,but the interference of impurity ions increases the difficulty of extracting lithium ions.Therefore,we prepared an imidazole-based ionic liquid(1-butyl-3-methylImidazolium bis(trifluoromethyl sulfonyl)imide)(IL)for efficient lithium extraction from aqueous solutions by solvent extraction.Using an extraction consisting of 10%IL,85% tributyl phosphate(TBP),and 5% dichloroethane and an organic to aqueous phase ratio(O/A)of 2/1,over 64.23% of Li were extracted,and the extraction rate after five-stage extraction could reach more than 96%.The addition of ammonium ions to the solution inhibited the extraction of Ni,and the separation coefficient between lithium and nickel approached infinity,showing a very perfect separation effect.Fouriertransform infrared spectroscopy and slope methods were used to analyze the changes that occurred during extraction,revealing possible extraction mechanisms.In addition,the LiCl solution generated during the preparation of ionic liquids was mixed with the stripping solution,and the battery-grade lithium carbonate was prepared by Na_(2)CO_(3) precipitation,with a purity of 99.74%.This study provides an efficient and sustainable strategy for recovering lithium from the solution.
基金supported by the National Natural Science Foundation of China(22278202)the Natural Science Foundation of Jiangsu Province(BM2018007.BK20210185).
文摘The transformation of CO_(2)into high value-added product is a promising pathway for utilizing CO_(2).However,the process tends to require harsh reaction conditions owing to CO_(2)chemical inertness.Designing a high efficiency catalytic system with environmentally benign characteristic are important determinants.In this work,protic ionic liquids[TMG][2-OPy]were prepared via one-step neutralization between 1,1,3,3-tetramethylguanidine and 2-hydroxypyridine,applying to the domain of synthesizing quinzoline-2,4(1 H,3H)-diones from CO_(2)and 2-aminobenzontiles without any solvent or metal,achieving the yield of 97%at 90℃for 8 h under atmospheric.A series of substrates with good to acceptable yield were detected,revealing the generality and universality of the catalyst.Furthermore,the system could be facilely reused for at least six runs,retaining the yield of 94%.A preliminary kinetic equation is calculated with the activation energy of 68 kJ·mol^(-1),and a plausible reaction mechanism was put forward.This study highlights that the[TMG][2-OPy]enables to activate CO_(2)carboxylation efficiently.
基金financial support from the National Natural Science Foundation of China(22075094)the Fundamental Research Funds for the Central Universities。
文摘Metal halide perovskite solar cells(PSCs)have shown great potential to become the next generation of photovoltaic devices due to their simple fabrication techniques,low cost,and soaring power conversion efficiency(PCE).However,mismatched with the quickly updated PCEs,the improvement of device stability is challenging and still remains a critical hurdle in the path to commercialization.Recently,ionic liquids(ILs)have been found to play multiple roles in obtaining efficient and stable PSCs.These ILs usually consist of large organic cations and organic or inorganic anions,which have weak electrostatic attraction and are generally liquid at around 100℃.ILs are almost non-volatile,non-flammable,with high ionic conductivity and excellent thermal and electrochemical stability.The roles of ILs in PSCs vary with their composition,that is,the types of anions and cations.In this review,we summarize the roles of anions and cations in terms of precursor solutions,additives,perovskite/charge transport layer interface engineering,and charge transport layers.This article aims to set up a structure–property-stability-performance correlations conferred by the IL in PSC and provide assistance for the anion and cation selection for improving the quality of perovskite film,optimizing interface contact,reducing defect states,and improving charge extraction and transport characteristics.Finally,the application of IL in PSCs is discussed and prospected.
基金support from the National Natural Science Foundation of China(No.21808048 and U1704251)Training Plan for University's Young Backbone Teachers of Henan Province(2021GGJS121)+5 种基金Program for Science&Technology Innovation Talents in Universities of Henan Province(23HASTIT014)Postgraduate Education Reform and Quality Improvement Project of Henan Province(YJS2022KC22)Project funded by China Postdoctoral Science Foundation(No.2018M632782)Project funded by Postdoctoral Research Grant in Henan Province(No.001802030)Key Project of Science and Technology Program of Henan Province(No.222102230109,212102310330 and 182102210050)the Science Research Start-up Fund of Henan Institute of Science and Technology(No.2015031).
文摘Diphenyl carbonate(DPC)is one of the versatile carbonates,and is often used for the production of polycarbonates.In recent years,the catalytic synthesis of DPC has become an important topic but the development of a highly active metal-free catalyst is a great challenge.Herein,a series of ionic liquids-SBA-15 hybrid catalysts with different functional groups have been developed for the synthesis of DPC under solventfree condition,which are effective and clean instead of the metal-containing catalysts.It is found that in the presence of[SBA-15-IL-OH]Br catalyst,methyl phenyl carbonate(MPC)conversion of 80.5%along with 99.6%DPC selectivity is achieved,the TOF value is thrice higher than the best value reported by using transition metal-based catalysts.Moreover,the catalyst displays remarkable stability and recyclability.This work provides a new idea to design and prepare eco-friendly catalysts in a broad range of applications for the green synthesis of carbonates.
基金financially supported by the National Natural Science Foundation of China(21875265,22293015,22121002)。
文摘Phenol in waste water threatens human health and is difficultly to be decomposed by nature.Efficient degradation of high-loaded phenol in water under mild condition is still a great challenge.Herein,ionic liquids with tungstate anion were designed and prepared.It was found that dodecyltrimethylammonium tungstate could catalyzed degradation of phenol into gases and water thoroughly at 323 k in 8 h.Tungstate anion revealed good catalytic oxidative activity and long carbon chain group connecting with cation of ionic liquids enriched phenol around catalysts,which induced the complete degradation of phenol at mild conditions.Increasing the amounts of hydrogen peroxide benefited to the total degradation of phenol.In addition,the ionic liquid could be reused for its excellent thermal stability.Our work provided a different strategy to treat waste water containing phenol efficiently.
基金supported by National Natural Science Foundation of China(42074142,51527805)。
文摘The hydrodynamic study of the liquid film around Taylor bubbles in slug flow has great significance for understanding parallel flow and interaction between Taylor bubbles.The prediction models for liquid film thickness mainly focus on stagnant flow,and some of them remain inaccurate performance.However,in the industrial process,the slug flow essentially is co-current flow.Therefore,in this paper,the liquid film thickness is studied by theoretical analysis and experimental methods under two conditions of stagnant and co-current flow.Firstly,under the condition of stagnant flow,the present work is based on Batchelor's theory,and modifies Batchelor's liquid film thickness model,which effectively improves its prediction accuracy.Under the condition of co-current flow,the prediction model of average liquid film thickness in slug flow is established by force and motion analysis.Taylor bubble length is introduced into the model as an important parameter.Dynamic experiments were carried out in the pipe with an inner diameter of 20 mm.The liquid film thickness,Taylor bubble velocity and length were measured by distributed ultrasonic sensor and intrusive cross-correlation conductivity sensor.Comparing the predicted value of the model with the measured results,the relative error is controlled within 10%.
基金supported by the National Natural Science Foundation of China (Grant No.22278271)the Key Project of Education Department of Liaoning Province(Grant No.LZGD2020005)
文摘Metal-organic frameworks(MOFs)have attracted considerable research attention as a new type of porous material for catalytic applications.Herein,2,5-dihydroxyterephthalic acid was proposed to replace conventional terephthalic acid and reacted with chromic nitrate nonahydrate to synthesize a functional metal–organic framework(FMIL-101).This was then used to immobilize various compound ionic liquids to prepare three ionic liquids immobilized on FMIL-101 catalysts,namely,FMIL-101-[HeMIM]Cl/(ZnBr_(2))_(2),FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),and FMIL-101-[AeMIM]Br/(ZnBr_(2))_(2).After characterization by Fourier-transform infrared spectroscopy,X-ray diffraction,ultraviolet spectroscopy,thermogravimetry,specific surface area analysis,and scanning electron microscopy,the catalysts were used to mediate cycloaddition reactions between carbon dioxide(CO_(2))and propylene oxide.The effects of reaction temperature,reaction pressure,reaction time,and catalyst dosage on the catalytic performance were investigated.The results revealed that the FMIL-101-supported CIL catalysts afforded the target product propylene carbonate with good catalytic performance and thermal stability.The optimal catalyst,FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),displayed a propylene oxide conversion of 98.64%and a propylene carbonate selectivity of 96.63%at a reaction temperature of 110℃,a reaction pressure of 2.0 MPa,a catalyst dosage of 2.0%relative to propylene oxide,and a reaction time of 2.5 h.In addition,the conversion and selectivity of the catalyst decreased slightly after four cycles.Additionally,the catalyst decreased slightly in catalytic performance after being recycled four times.
基金Supported by the National Natural Science Foundation of China(No.21725603)Zhejiang Provincial Natural Science Foundation of China(LZ18B060001)the National Program for Support of Top-notch Young Professionals(H.X.)
文摘Light hydrocarbons(C1–C4) are fundamental raw materials in the petroleum and chemical industry. Separation and purification of structurally similar paraffin/olefin/alkyne mixtures are important for the production of highpurity or even polymer-grade light hydrocarbons. However, traditional methods such as cryogenic distillation and solvent absorption are energy-intensive and environmentally unfriendly processes. Ionic liquids(ILs) as a new alternative to organic solvents have been proposed as promising green media for light hydrocarbon separation due to their unique tunable structures and physicochemical properties resulting from the variations of the cations and anions such as low volatility, high thermal stability, large liquidus range, good miscibility with light hydrocarbons, excellent molecular recognition ability and adjustable hydrophylicity/hydrophobicity. In this review, the recent progresses on the light hydrocarbon separation using ILs are summarized, and some parameters of ILs that influence the separation performance are discussed.
基金Supported by the National Key Projects for Fundamental Research and Development of China(2016YFB0600305).
文摘Low temperature coal tar contained a large amount of phenols, aromatic hydrocarbons and alkanes;the separation of phenols from coal tar has a great significance to the deep processing of coal tar. In this work, the separation of m-cresol from cumene and n-heptane by liquid–liquid extraction using ionic liquids(ILs) as extractants was studied. The suitable ILs were screened by conductor-like screening model for real solvents(COSMO-RS)model and the liquid–liquid phase equilibrium(LLE) experiments were to verify the accuracy of the screening results. The extraction conditions such as extraction time, extraction temperature and mass ratio of ILs to model oils were evaluated. An internal mechanism of the m-cresol extract by ILs was revealed by COSMO-RS calculation and FT-IR. The results showed that the selected ILs can extract m-cresol effectively from cumene and nheptane, 1-ethyl-3-methylimidazolium acetate(emim CH3 COO) was the best extraction solvent. A hydrogen bond between anion of ILs and phenolic hydroxyl groups was observed. M-cresol in model oils could be extracted with extraction efficiencies up to 98.85% at an emim CH3 COO: model oils mass ratio of 0.5 and 298.15 K,emim CH3 COO could be regenerated and reused for 4 cycles without obvious decreases in extraction efficiency and extractant mass.
基金The financial support from National Natural Science Foundation of China(21978096,21861132019,and 21776074)Natural Science Foundation of Shanghai(19ZR1412600)is greatly acknowledged
文摘1,5-Pentanediamine(PDA)produced by biological fermentation becomes popular,but the separation of PDA from the broth is a typical difficult problem.In this work,the performance of 200 ionic liquids(ILs),formed by combining 25 cations and 8 anions,in the extraction of PDA from aqueous solution were evaluated using COSMO-RS model.The extraction mechanism was investigated with the help ofσ-profile and interaction energy analyses.Both the cation and anion have impacts on the extraction efficiency,where cation mainly influences the interaction of IL with PDA and anion affects the hydrophobicity of IL.The IL composed of long alkyl-chain in cation and the anion of[PF6]-or[TF2 N]-,which has theσ-profile more likely distributed in the nonpolar region but less distributed in the polar region,is favorable for extraction.The experimental liquid-liquid equilibrium demonstrated the effects of cation and anion on extraction performance,which validated the reliability of COSMO-RS model in IL screening for PDA extraction.The IL[IM-1,8][PF6]could serve as a promising extractant for the downstream separation process of the biological production of PDA.
基金supported by the National Natural Science Foundation of China (21606233, 21436010)the National Natural Science Fund for Distinguished Young Scholars (21425625)the Research Council of Norway through the CLIMIT program (215732)
文摘CO_2 capture with ionic liquids(ILs) has attracted many attentions, and most works focused on absorption ability at ambient temperatures, while seldom research was concerned at elevated temperatures.This not only limits the CO_2 absorption application at elevated temperature, but also the determination of the operation condition of the CO_2 desorption generally occurring at higher temperature. This work mainly reported CO_2 solubilities in ILs at elevated temperatures and related properties were also provided. 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide([CnMIm][Tf_2N]) ILs were selected as physical absorbents for CO_2 capture in this work due to their relative higher CO_2 absorption capacities and good thermal stabilities. The long-term stability tests showed that [CnMIm][Tf_2N] is thermally stable at 393.15 K for long time. CO_2 solubilities in [CnMIm][Tf_2N] were systematically determined at temperatures from 353.15 K to 393.15 K. It demonstrated that CO_2 solubility obviously increases with the increase of pressure while slightly decreases with increase of temperature. As the length of alkyl chain on the cation increases, CO_2 solubility in ILs increases. Additionally, the thermodynamic properties including the Gibbs free energy, enthalpy, and entropy of CO_2 were also calculated.
文摘High spatial frequency laser induced periodic surface structures(HSFLs)on silicon substrates are often developed on flat surfaces at low fluences near ablation threshold of 0.1 J/cm2,seldom on microstructures or microgrooves at relatively higher fluences above 1 J/cm^2.This work aims to enrich the variety of HSFLs-containing hierarchical microstructures,by femtosecond laser(pulse duration:457 fs,wavelength:1045 nm,and repetition rate:100 kHz)in liquids(water and acetone)at laser fluence of 1.7 J/cm^2.The period of Si-HSFLs in the range of 110–200 nm is independent of the scanning speeds(0.1,0.5,1 and 2 mm/s),line intervals(5,15 and 20μm)of scanning lines and scanning directions(perpendicular or parallel to light polarization direction).It is interestingly found that besides normal HSFLs whose orientations are perpendicular to the direction of light polarization,both clockwise or anticlockwise randomly tilted HSFLs with a maximal deviation angle of 50°as compared to those of normal HSFLSs are found on the microstructures with height gradients.Raman spectra and SEM characterization jointly clarify that surface melting and nanocapillary waves play important roles in the formation of Si-HSFLs.The fact that no HSFLs are produced by laser ablation in air indicates that moderate melting facilitated with ultrafast liquid cooling is beneficial for the formation of HSFLs by LALs.On the basis of our findings and previous reports,a synergistic formation mechanism for HSFLs at high fluence was proposed and discussed,including thermal melting with the concomitance of ultrafast cooling in liquids,transformation of the molten layers into ripples and nanotips by surface plasmon polaritons(SPP)and second-harmonic generation(SHG),and modulation of Si-HSFLs direction by both nanocapillary waves and the localized electric field coming from the excited large Si particles.
基金supported by National 863 High-Tech Research and Development Program of China(No. 2007AA05Z101)
文摘In this article,an efficient,simple and environmentally friendly approach to the synthesis of diacetals（diketals） pentaerythritol using SO<sub>3</sub>H-functionalized ionic liquids（ILs） as catalysts was reported.The ILs show high catalytic activity and reusability with good to excellent yields of the desired products.Hammett method has been used to determine the acidity order of these ionic liquids and the results are consistent with the catalytic activities observed in acetalization reaction.Maximum product yield of 93%was observed on using[PSPy][OTf]as catalyst and it can be reused at least 8 times without obvious activity loss.
基金the National Natural Science Foundation of China(21503131 and 51711530162)the Shanghai Municipal Science and Technology Commission(19640770300)+2 种基金the Shanghai Engineering Research Center of New Materials and Application for Resources and Environment(18DZ2281400)the Professional and Technical Service Platform for Designing and Manufacturing of Advanced Composite Materials(Shanghai)(19DZ2293100)the Engineering Research Center of Material Composition and Advanced Dispersion Technology,Ministry of Education。
文摘The pursuit of high energy density has promoted the development of high-performance lithium metal batteries.However,it faces a serious security problem.Ionic liquids have attracted great attention due to their high ionic conductivity,non-flammability,and the properties of promoting the formation of stable SEI films.Deeply understanding the problems existing in lithium metal batteries and the role of ionic liquids in them is of great significance for improving the performance of lithium metal batteries.This article reviews the effects of the molecular structure of ionic liquids on ionic conductivity,Li^(+)ion transference number,electrochemical stability window,and lithium metal anode/electrolyte interface,as well as the application of ionic liquids in Li-high voltage cathode batteries,Li-O_(2) batteries and Li-S batteries.The molecular design,composition and polymerization will be the main strategies for the future development of ionic liquid-based electrolytes for high performance lithium metal battery.
基金Supported by the National Natural Sciences Foundation of China(91434107,21506232)National Key Projects for Fundamental Research and Development of China(2016YFB0600903)
文摘A large number of surplus glycerol from the biodiesel production can be used as renewable feedstock to produce glycerol carbonate. In this paper, a series of guanidine-based ionic liquids were synthesized to catalyze the transesterification of glycerol and dimethyl carbonate. The tunable basicity and the anion–cation cooperative effect were responsible for the obtained results. The [TMG][TFE] showed the best activity turnover frequency(TOF)of 1754.0 h^(-1), glycerol(GL) conversion of 91.8%, glycerol carbonate(GC) selectivity of 95.5%) at 80 °C with 0.1 mol% catalyst for 30 min. The reaction mechanism of the transesterification was also proposed.
基金financially supported by the National Natural Science Foundation of China under Grants (Nos. 21476009, 21406007 and U1462104)
文摘The adjustable parameters in the popular conductor-like screening model for real solvents(COSMO-RS)within the Amsterdam density functional(ADF)framework have been re-optimized to fit for the systems containing ionic liquids(ILs).To get the optimal values of misfit energy constant a^0,hydrogen bond coefficient c_(hb)and effective contact surface area of a segment a_(eff),2283 activity coefficient data points at infinite dilution and 1433 CO_2 solubility data points exhaustively collected from references were used as training set.The average relative deviations(ARDs)of activity coefficients at infinite dilution and CO_2 solubility between experimental data and predicted values are 32.22%and17.61%,respectively,both of which are significantly lower than the original COSMO-RS versions.Predictions for other activity coefficients of solutes in ILs,solubility data of CO_2 in pure ILs and the binary mixtures of ILs at either high or low temperatures,and vapor–liquid equilibrium(VLE)for binary systems involving ILs have also been performed to demonstrate the validity of the parameterization of COSMO-RS model for ILs.The results showed that the predicted results by COSMO-RS model with the new optimized parameters are in much better agreement with experimental data than those by the original versions over a wide temperature and pressure range.The COSMO-RS model for ILs presented in this work improves the prediction accuracy of thermodynamic properties for the systems containing ILs,which is always highly desirable for general chemical engineers.
基金partially supported by the Grant-inAid for Scientific Research A(24241023)Grant-in-Aid for Challenging Exploratory Research(17K19139)from the Japan Society for the Promotion of Science
文摘Polyamide 6 underwent an efficient depolymerization in hydrophilic ionic liquids under microwave irradiation at 300C. The depolymerization completed within 60 min. Caprolactam was readily separated by simple extraction procedure and the ionic liquids were recovered and reused for several times. Addition of catalytic amounts of DMAP(N,N-dimethylaminopyridine) promoted the depolymerization effectively.The present improved procedure provides a method to avoid direct distillation procedure, which consumes energy for the separation of caprolactam from ionic liquids. Although some contamination of ionic liquids was observed, the present procedure provides a new possibility for the use of ionic liquids for plastic chemical recycling from the viewpoint of development of an energy-saving methodology. Use of solubility switchable ionic liquids is also examined to explore a possibility for better separation although depolymerization did not work well.
