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 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
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
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
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
We synthesized one quaternary ammonium polymeric ionic liquids(PILs)P[VBTHEA]Cl and three imidazolium PILs of P[VEIm]Br, P[VEIm]BF_4, P[VEIm]PF_6 by free-radical polymerization in solution. These PILs were characteriz...We synthesized one quaternary ammonium polymeric ionic liquids(PILs)P[VBTHEA]Cl and three imidazolium PILs of P[VEIm]Br, P[VEIm]BF_4, P[VEIm]PF_6 by free-radical polymerization in solution. These PILs were characterized by FT-IR,~1 H-NMR,^(13)C-NMR, TGA, XRD and SEM. Their CO_2 adsorption capacities were measured under different pressures and temperatures by constant-volume technique. It was observed that quaternary ammonium PILs of P[VBTHEA]Cl have higher adsorption capacity for CO_2 than those imidazolium PILs, following P[VBTHEA]Cl > P[VEIm]PF_6> P[VEIm]BF_4> P[VEIm]Br, which may be ascribed to higher positive charge density on ammonium cation than that on imidazolium cation and thus stronger interaction with CO_2, consistent with the results from dual-mode adsorption model that ammonium PILs have much higher CO_2 bulk absorption than imidazolium PILs. CO_2 adsorption capacity of P[VBTHEA]Cl is 9.02 mg/g under 295 K and 1 bar, which is comparable to that of some other PILs, and is much higher than that of the corresponding ILs monomer. These PILs have good adsorption selectivity for CO_2 over N_2 and regeneration efficiency.展开更多
An efficient method for prediction in the capture of SO_(2)from flue gas by imidazolium ionic liquids was reported,where the concentration of SO_(2)is 2000 ppm.On the basis of quantitative calculations through a combi...An efficient method for prediction in the capture of SO_(2)from flue gas by imidazolium ionic liquids was reported,where the concentration of SO_(2)is 2000 ppm.On the basis of quantitative calculations through a combination of Langmuir simulation,theoretical calculation and quantum chemical method,SO_(2)absorption and desorption performance from flue gas by twelve kinds of imidazolium ionic liquids with different anions were designed and predicted.Then,among them,five kinds of imidazolium ionic liquids were chosen and prepared to investigate their behavior of SO_(2)absorption capacity,desorption residue,and available absorption capacity.The results indicated that the experimental values were in good agreement with the predicted values.Thus,an ideal ionic liquid[Emim][Tetz]was obtained through the predictive method for the capture of SO_(2)of 2000 ppm,which showed high available absorption capacity of 0.24 g SO_(2)per g ionic liquid and excellent reversibility.展开更多
Five Br?nsted acidic ionic liquids(ILs) were prepared and characterized by FT-IR,~1H NMR and ^(13)C NMR. Their catalytic activities for the synthesis of 2-propanol(IPOH) via transesterification of isopropyl acetate(IP...Five Br?nsted acidic ionic liquids(ILs) were prepared and characterized by FT-IR,~1H NMR and ^(13)C NMR. Their catalytic activities for the synthesis of 2-propanol(IPOH) via transesterification of isopropyl acetate(IPAc) with methanol(Me OH) were investigated. Among all the tested ILs, [Ps-mim]HSO_4 performed best and was used as catalyst for further studies. The reaction kinetics were carried out to correlate the parameters in a homogeneous second order kinetic model. It has been found that there is close agreement between the calculated and experimental values. The high-pressure batch reactive distillation experimental apparatus was set up in order to enhance the conversion of IPAc. A high conversion of IPAc of 99.4% was obtained under the optimal reaction conditions. The catalyst [Ps-mim]HSO_4 can be recycled easily by a rotary evaporator and reused without any further treatment. The catalyst had been repeatedly used for four times and no obvious changes in the structure of catalyst could be observed.展开更多
The potential applications of shale oil as a substitute energy source are adversely influenced due to its high nitrogen content.In this work,four imidazolium ionic liquids(ILs),i.e.,1-butyl-3-methylimidazolium chlorid...The potential applications of shale oil as a substitute energy source are adversely influenced due to its high nitrogen content.In this work,four imidazolium ionic liquids(ILs),i.e.,1-butyl-3-methylimidazolium chloride([Bmim]Cl),1-butyl-3-methylimidazolium acetate([Bmim]Ac),1-butyl-3-methylimidazolium acetate/ZnAc2([Bmim]Ac/ZnAc2)and 1-butyl-3-methylimidazolium chloride/ZnAc2([Bmim]Cl/ZnAc2),were used to extract the basic nitrides and neutral nitrides from shale oil.The influence of extraction time,temperature,properties of N-compounds,ILs structure,mass ratio of IL/oil,multiple cycles of denitrogenation,physical mixing of ILs and ILs recyclability on extractive denitrogenation was systematically investigated.The denitrogenation performance of all ILs was determined and investigated from micro-level view withσ-profile.It was observed that,ILs composed of anions with weaker HB acceptor capacity,have the higher N-extraction efficiency to the neutral nitrogen compounds with weaker HB acceptor capacity.More than 96%N-extraction efficiency was achieved at the end of a single extraction cycle for time<10 min under 40℃C and 1:1 of IL:oil(w/w),especially 100%N-extraction efficiency was realized for carbazole and indole.The N-extraction efficiency up to 60.1%and 53.7%for real shale oil was realized by[Bmim]Ac and[Bmim]Ac/ZnAc2,respectively,which are about 10%better than other non-hydrodenitrogenation technologies.Moreover,[Bmim]Ac and[Bmim]Ac/ZnAc2 exhibited almost the same extractive denitrogenation performance after regeneration.This work has developed a new approach to lessen the nitrogen content of shale oil effectively and economically.展开更多
As green solvents,ionic liquids(ILs)are quite suitable for the absorption of volatile organic compounds(VOCs)such as benzene and its homologues.However,solvent selection is the key to the VOC absorption process.In the...As green solvents,ionic liquids(ILs)are quite suitable for the absorption of volatile organic compounds(VOCs)such as benzene and its homologues.However,solvent selection is the key to the VOC absorption process.In the present study,a rapid solvent screening tool,Conductor-like Screening Model for Real Solvents(COSMO-RS),was used to predict the solubility of toluene in 816 ILs.The effects of four structure characters,namely,the type and alkyl chain length of the cations and anions on the solubility of toluene were discussed.The following conclusions were drawn from the results:(1)ILs with pyrrolidinium-based cations showed better solubility than pyridinium-and imidazoliumbased ones.(2)The solubility of toluene in PF6-based ILs increased with the increasing alkyl chain length,while its solubility in Ac-based ILs exhibited the opposite trend.(3)Toluene showed greater solubility in Cl-based ILs than those based on other anions.(4)The solubility of toluene increased with the anion alkyl chain length.Ac-based ILs were chosen as the most promising potential solvents,and further studied to determine the relationship between various interaction energy parameters and toluene solubility.The results showed that the misfit energy played a dominant role during the absorption process.Furthermore,several ILs were selected for experimental verification of the predicted solubility behavior using liquid and gaseous toluene.The results demonstrated that COSMO-RS could be used to semi-quantitatively and qualitatively predict the solubility of toluene,and this model had promising prospects in screening ILs for VOCs absorption.In summary,this study provided a fundamental basis and practical data for the control and treatment of VOCs.展开更多
A membrane contactor using ionic liquids(ILs) as solvent for pre-combustion capture CO_2 at elevated temperature(303-393 K) and pressure(20 bar) has been studied using mathematic model in the present work. A comprehen...A membrane contactor using ionic liquids(ILs) as solvent for pre-combustion capture CO_2 at elevated temperature(303-393 K) and pressure(20 bar) has been studied using mathematic model in the present work. A comprehensive two-dimensional(2 D) mass-transfer model was developed based on finite element method. The effects of liquid properties, membrane configurations, as well as operation parameters on the CO_2 removal efficiency were systematically studied. The simulation results show that CO_2 can be effectively removed in this process. In addition, it is found that the liquid phase mass transfer dominated the overall mass transfer. Membranes with high porosity and small thickness could apparently reduce the membrane resistance and thus increase the separation efficiency. On the other hand, the membrane diameter and membrane length have a relatively small influence on separation performance within the operation range.展开更多
The absorption of CO_(2)is of importance in carbon capture,utilization,and storage technology for greenhouse gas control.In the present work,we clarified the mechanism of how metal-based ionic liquids (MBILs),Bmim[XCl...The absorption of CO_(2)is of importance in carbon capture,utilization,and storage technology for greenhouse gas control.In the present work,we clarified the mechanism of how metal-based ionic liquids (MBILs),Bmim[XCl_(n)]_(m)(X is the metal atom),enhance the CO_(2)absorption capacity of ILs via performing molecular dynamics simulations.The sparse hydrogen bond interaction network constructed by CO_(2)and MBILs was identified through the radial distribution function and interaction energy of CO_(2)-ion pairs,which increase the absorption capacity of CO_(2)in MBILs.Then,the dynamical properties including residence time and self-diffusion coefficient confirmed that MBILs could also promote the diffusion process of CO_(2)in ILs.That's to say,the MBILs can enhance the CO_(2)absorption capacity and the diffusive ability simultaneously.Based on the analysis of structural,energetic and dynamical properties,the CO_(2)absorption capacity of MBILs increases in the order Cl^-→[ZnCl_(4)]^(2-)→[CuCl_(4)]^(2-)→[CrCl_(4)]^-→[FeCl_(4)]^-,revealing the fact that the short metal–Cl bond length and small anion volume could facilitate the performance of CO_(2)absorbing process.These findings show that the metal–Cl bond length and effective volume of the anion can be the effective factors to regulate the CO_(2)absorption process,which can also shed light on the rational molecular design of MBILs for CO_(2)capture and other key chemical engineering processes,such as IL-based gas sensors,nano-electrical devices and so on.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 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.
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financially supported by State Key Laboratory of Organic-Inorganic Composites(oic-201601012)the International Scientific Partnership Program ISPP at King Saud University for funding this research work through ISPP#0080
文摘We synthesized one quaternary ammonium polymeric ionic liquids(PILs)P[VBTHEA]Cl and three imidazolium PILs of P[VEIm]Br, P[VEIm]BF_4, P[VEIm]PF_6 by free-radical polymerization in solution. These PILs were characterized by FT-IR,~1 H-NMR,^(13)C-NMR, TGA, XRD and SEM. Their CO_2 adsorption capacities were measured under different pressures and temperatures by constant-volume technique. It was observed that quaternary ammonium PILs of P[VBTHEA]Cl have higher adsorption capacity for CO_2 than those imidazolium PILs, following P[VBTHEA]Cl > P[VEIm]PF_6> P[VEIm]BF_4> P[VEIm]Br, which may be ascribed to higher positive charge density on ammonium cation than that on imidazolium cation and thus stronger interaction with CO_2, consistent with the results from dual-mode adsorption model that ammonium PILs have much higher CO_2 bulk absorption than imidazolium PILs. CO_2 adsorption capacity of P[VBTHEA]Cl is 9.02 mg/g under 295 K and 1 bar, which is comparable to that of some other PILs, and is much higher than that of the corresponding ILs monomer. These PILs have good adsorption selectivity for CO_2 over N_2 and regeneration efficiency.
基金supported by the National Key Basic Research Program of China(2015CB251401)the National Natural Science Foundation of China(21776235)+1 种基金the Zhejiang Provincial Natural Science Foundation of China(LZ17B060001)the Fundamental Research Funds for the Central Universities
文摘An efficient method for prediction in the capture of SO_(2)from flue gas by imidazolium ionic liquids was reported,where the concentration of SO_(2)is 2000 ppm.On the basis of quantitative calculations through a combination of Langmuir simulation,theoretical calculation and quantum chemical method,SO_(2)absorption and desorption performance from flue gas by twelve kinds of imidazolium ionic liquids with different anions were designed and predicted.Then,among them,five kinds of imidazolium ionic liquids were chosen and prepared to investigate their behavior of SO_(2)absorption capacity,desorption residue,and available absorption capacity.The results indicated that the experimental values were in good agreement with the predicted values.Thus,an ideal ionic liquid[Emim][Tetz]was obtained through the predictive method for the capture of SO_(2)of 2000 ppm,which showed high available absorption capacity of 0.24 g SO_(2)per g ionic liquid and excellent reversibility.
基金Supported by the National Natural Science Foundation of China(21576053,91534106,21306025)the International S&T Cooperation Program of China(2013DFR90540)+3 种基金the Science Foundation of Distinguished Young Scholars of Fujian(2014J06004)the New Century Excellent Talents in Fujian Province University(JA12014)the Natural Science Foundation of Fujian Province(2016J01689)the Key Project of Fujian Provincial Department of Science and Technology(2014Y0066)
文摘Five Br?nsted acidic ionic liquids(ILs) were prepared and characterized by FT-IR,~1H NMR and ^(13)C NMR. Their catalytic activities for the synthesis of 2-propanol(IPOH) via transesterification of isopropyl acetate(IPAc) with methanol(Me OH) were investigated. Among all the tested ILs, [Ps-mim]HSO_4 performed best and was used as catalyst for further studies. The reaction kinetics were carried out to correlate the parameters in a homogeneous second order kinetic model. It has been found that there is close agreement between the calculated and experimental values. The high-pressure batch reactive distillation experimental apparatus was set up in order to enhance the conversion of IPAc. A high conversion of IPAc of 99.4% was obtained under the optimal reaction conditions. The catalyst [Ps-mim]HSO_4 can be recycled easily by a rotary evaporator and reused without any further treatment. The catalyst had been repeatedly used for four times and no obvious changes in the structure of catalyst could be observed.
基金This work was financially supported by the Natural Science Foundation of China(21176021,21276020)the China postdoctoral science foundation(2018M641164)+1 种基金We extend our appreciation to the Natural Science Foundation of China(21176021,21276020)China postdoctoral science foundation(2018M641164)for funding the work.
文摘The potential applications of shale oil as a substitute energy source are adversely influenced due to its high nitrogen content.In this work,four imidazolium ionic liquids(ILs),i.e.,1-butyl-3-methylimidazolium chloride([Bmim]Cl),1-butyl-3-methylimidazolium acetate([Bmim]Ac),1-butyl-3-methylimidazolium acetate/ZnAc2([Bmim]Ac/ZnAc2)and 1-butyl-3-methylimidazolium chloride/ZnAc2([Bmim]Cl/ZnAc2),were used to extract the basic nitrides and neutral nitrides from shale oil.The influence of extraction time,temperature,properties of N-compounds,ILs structure,mass ratio of IL/oil,multiple cycles of denitrogenation,physical mixing of ILs and ILs recyclability on extractive denitrogenation was systematically investigated.The denitrogenation performance of all ILs was determined and investigated from micro-level view withσ-profile.It was observed that,ILs composed of anions with weaker HB acceptor capacity,have the higher N-extraction efficiency to the neutral nitrogen compounds with weaker HB acceptor capacity.More than 96%N-extraction efficiency was achieved at the end of a single extraction cycle for time<10 min under 40℃C and 1:1 of IL:oil(w/w),especially 100%N-extraction efficiency was realized for carbazole and indole.The N-extraction efficiency up to 60.1%and 53.7%for real shale oil was realized by[Bmim]Ac and[Bmim]Ac/ZnAc2,respectively,which are about 10%better than other non-hydrodenitrogenation technologies.Moreover,[Bmim]Ac and[Bmim]Ac/ZnAc2 exhibited almost the same extractive denitrogenation performance after regeneration.This work has developed a new approach to lessen the nitrogen content of shale oil effectively and economically.
基金supported by the National Natural Science Foundation of China(51474146,21806102)Graduate Program Funding of Shanghai Polytechnic University(A01GY18F022-d04,EGD18YJ0004)Gaoyuan Discipline of Shanghai–Environmental Science and Engineering(Resource Recycling Science and Engineering)
文摘As green solvents,ionic liquids(ILs)are quite suitable for the absorption of volatile organic compounds(VOCs)such as benzene and its homologues.However,solvent selection is the key to the VOC absorption process.In the present study,a rapid solvent screening tool,Conductor-like Screening Model for Real Solvents(COSMO-RS),was used to predict the solubility of toluene in 816 ILs.The effects of four structure characters,namely,the type and alkyl chain length of the cations and anions on the solubility of toluene were discussed.The following conclusions were drawn from the results:(1)ILs with pyrrolidinium-based cations showed better solubility than pyridinium-and imidazoliumbased ones.(2)The solubility of toluene in PF6-based ILs increased with the increasing alkyl chain length,while its solubility in Ac-based ILs exhibited the opposite trend.(3)Toluene showed greater solubility in Cl-based ILs than those based on other anions.(4)The solubility of toluene increased with the anion alkyl chain length.Ac-based ILs were chosen as the most promising potential solvents,and further studied to determine the relationship between various interaction energy parameters and toluene solubility.The results showed that the misfit energy played a dominant role during the absorption process.Furthermore,several ILs were selected for experimental verification of the predicted solubility behavior using liquid and gaseous toluene.The results demonstrated that COSMO-RS could be used to semi-quantitatively and qualitatively predict the solubility of toluene,and this model had promising prospects in screening ILs for VOCs absorption.In summary,this study provided a fundamental basis and practical data for the control and treatment of VOCs.
基金partly supported by the Research Council of Norway through CLIMIT program (MCIL-CO_2 project, 215732)
文摘A membrane contactor using ionic liquids(ILs) as solvent for pre-combustion capture CO_2 at elevated temperature(303-393 K) and pressure(20 bar) has been studied using mathematic model in the present work. A comprehensive two-dimensional(2 D) mass-transfer model was developed based on finite element method. The effects of liquid properties, membrane configurations, as well as operation parameters on the CO_2 removal efficiency were systematically studied. The simulation results show that CO_2 can be effectively removed in this process. In addition, it is found that the liquid phase mass transfer dominated the overall mass transfer. Membranes with high porosity and small thickness could apparently reduce the membrane resistance and thus increase the separation efficiency. On the other hand, the membrane diameter and membrane length have a relatively small influence on separation performance within the operation range.
基金financial support of the National Science Foundation of China(No.21808220)。
文摘The absorption of CO_(2)is of importance in carbon capture,utilization,and storage technology for greenhouse gas control.In the present work,we clarified the mechanism of how metal-based ionic liquids (MBILs),Bmim[XCl_(n)]_(m)(X is the metal atom),enhance the CO_(2)absorption capacity of ILs via performing molecular dynamics simulations.The sparse hydrogen bond interaction network constructed by CO_(2)and MBILs was identified through the radial distribution function and interaction energy of CO_(2)-ion pairs,which increase the absorption capacity of CO_(2)in MBILs.Then,the dynamical properties including residence time and self-diffusion coefficient confirmed that MBILs could also promote the diffusion process of CO_(2)in ILs.That's to say,the MBILs can enhance the CO_(2)absorption capacity and the diffusive ability simultaneously.Based on the analysis of structural,energetic and dynamical properties,the CO_(2)absorption capacity of MBILs increases in the order Cl^-→[ZnCl_(4)]^(2-)→[CuCl_(4)]^(2-)→[CrCl_(4)]^-→[FeCl_(4)]^-,revealing the fact that the short metal–Cl bond length and small anion volume could facilitate the performance of CO_(2)absorbing process.These findings show that the metal–Cl bond length and effective volume of the anion can be the effective factors to regulate the CO_(2)absorption process,which can also shed light on the rational molecular design of MBILs for CO_(2)capture and other key chemical engineering processes,such as IL-based gas sensors,nano-electrical devices and so on.
