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
Fischer indole cyclization of phenylhydrazine and various ketones using carboxyl-functionalized ionic liquid, 1-carboxymethyl- 3-methylimidazolium tetrafluoroborate (abbreviated as [crnmim] [BF4]) as catalyst was su...Fischer indole cyclization of phenylhydrazine and various ketones using carboxyl-functionalized ionic liquid, 1-carboxymethyl- 3-methylimidazolium tetrafluoroborate (abbreviated as [crnmim] [BF4]) as catalyst was successfully performed. The yields of the target compounds were 80-92%, the purities were 96-98%. The catalyst could be recovered and reused for at least six times without significant loss in activity.展开更多
In this article,an efficient,simple and environmentally friendly approach to the synthesis of diacetals(diketals) pentaerythritol using SOH-functionalized ionic liquids(ILs) as catalysts was reported.The ILs show high...In this article,an efficient,simple and environmentally friendly approach to the synthesis of diacetals(diketals) pentaerythritol using SOH-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 phosphine-functionalized phosphonium-based ionic liquids(dppm-Q, dppe-Q, dppp-Q and dppb-Q) as the bi-functional ligands enable the efficient one-pot tandem hydroformylationeacetalization. It was found that, in dp...The phosphine-functionalized phosphonium-based ionic liquids(dppm-Q, dppe-Q, dppp-Q and dppb-Q) as the bi-functional ligands enable the efficient one-pot tandem hydroformylationeacetalization. It was found that, in dppm-Q, dppe-Q, dppp-Q and dppb-Q, the incorporated phosphino-fragments were responsible for Rh-catalyzed hydroformylation and the phosphoniums were in charge of the subsequent acetalization as the Lewis acid catalysts. Moreover, the diphosphonium-based ionic liquid of dppb-DQ could be applied as a co-solvent to immobilize the Rh/dppb-Q catalytic system with the advantages of the improved catalytic performance, the available catalyst recyclability, and the wide generality for the substrates.展开更多
An innovative approach to H2 S capture has been developed using several metal-based ionic liquids([Bmim]Cl·CuCl_2, [Bmim]Cl·FeCl_3, [Bmim]Cl·ZnCl_2, [Bmim]Br·CuCl_2, and [Bmim]Br·FeCl_3) immob...An innovative approach to H2 S capture has been developed using several metal-based ionic liquids([Bmim]Cl·CuCl_2, [Bmim]Cl·FeCl_3, [Bmim]Cl·ZnCl_2, [Bmim]Br·CuCl_2, and [Bmim]Br·FeCl_3) immobilized on the sol-gel derived silica, which is superior to purely viscous ionic liquid with a crucial limit of high temperature, low mass transfer rate,and mass loss. The adsorbents were characterized by the Fourier transform infrared spectrometer, transmission electron microscope, N_2 adsorption/desorption, X-ray photoelectron spectroscopy, and thermal analysis techniques. The effects of the metal and halogen in IL, the loading amount of IL, and the adsorption temperature were studied by dynamic adsorption experiments at a gas flow rate of 100 mL/min. The H2 S adsorption results have showed that the optimal adsorbent and adsorption temperature are 5% [Bmim]Cl·CuCl_2/silica gel and 20—50 ℃, respectively. H_2 S can be captured and oxidized to elemental sulfur, and [Bmim]Cl·CuCl_2/silica gel can be readily regenerated by air. The excellent efficiency of H2 S removal may be attributed to the formation of nano-scaled and high-concentration [Bmim]Cl·CuCl_2 confined in silica gel, indicating that the immobilization of [Bmim]Cl·CuCl_2 on the sol-gel derived silica can be used for H2 S removal promisingly.展开更多
A series of functionalized ionic liquids (ILs) containing ester-group were synthesized and their tribological properties as lubricants for steel-steel contact were studied and compared with a non-functionalized ionic ...A series of functionalized ionic liquids (ILs) containing ester-group were synthesized and their tribological properties as lubricants for steel-steel contact were studied and compared with a non-functionalized ionic liquid and perfluoropolyethers (PFPE). The morphology and chemical composition of the worn scars were analyzed by scanning electron microscopy and X-ray photoelectron spectroscopy, respectively, and the possible lubrication mechanism of ILs was discussed. As a result, all ILs demonstrated a better lubricity and a much higher load-carrying capacity than PFPE used as lubricants for the steel-steel tribomates system. The functionalized ILs with ester-group showed slightly worse friction reducing ability than their nonfunctionalized counterparts at relatively lower loads owing to their higher viscosity, but then exhibited better antiwear ability because the ester group they contained had not only physical but also strong chemical reactions with the freshly exposed steel surface and formed chemical adsorption boundary films on the worn surface during friction process. Under high loads, some tribochemical reactions took place between the active elements, such as fluorine which were released from the ILs, and fresh metal surfaces of rubbing pairs to form the admixture reaction films, which were mainly composed of ferric fluoride mixed with ferric oxide, leading to lower friction coefficients and good wear resistance.展开更多
Room-temperature ionic liquids(ILs), which have excellent properties, such as high gas absorption abilities, extremely low volatility and tunable structures, are regarded as environmentally-friendly absorbents and wid...Room-temperature ionic liquids(ILs), which have excellent properties, such as high gas absorption abilities, extremely low volatility and tunable structures, are regarded as environmentally-friendly absorbents and widely used in SO_2 absorption and separation. As a result, a large number of ILs have been synthesized to capture SO_2 from flue gas or simulated gas, but a part of them just have physical interaction with SO_2 and can hardly absorb SO_2 when the content of SO_2 is very low. Hence, functional ILs, which can chemically absorb a large amount of SO_2 with low contents, have been designed and synthesized for SO_2 capture. Up to now, many kinds of functional ILs were investigated for SO_2 absorption from flue gas. In this review, the functional ILs are classified into guanidinium based ILs, hydroxyl ammonium based ILs, imidazolium/pyridinium based ILs, quaternary ammonium based ILs, phosphonium based ILs, and other kinds of ILs according to their cations. The capacities of SO_2 absorption in these ILs, the mechanism of the absorption, and the ways to enhance the absorption are briefly introduced. The prospect of functional ILs for their application in SO_2 removal is presented. The present problems and the further studies are also discussed.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
To obtain new functional aromatic polymer material, 3,3’-biacenaphthene, which is used as macromolecule intermediate of function aromatic polymer material, was synthesized through the coupling reaction of acenaphthen...To obtain new functional aromatic polymer material, 3,3’-biacenaphthene, which is used as macromolecule intermediate of function aromatic polymer material, was synthesized through the coupling reaction of acenaphthene catalyzing by ionic liquid ([bmim]Cl/FeCl3) at mild reaction condition. Pure 3,3’-biacenaphthene was obtained by recrystalling and column chromatography from the reaction mixture and was determined by GC/MS, 1HNMR and FTIR analysis. The influence of various reaction conditions on the yield of 3,3’-biacenaphthene were studied by GC analysis. The result shows that the optimum synthesis conditions of the coupling reaction are as following: the molar ratio of FeCl3 to [Bmim]Cl being 3, the mole ratio of FeCl3 in [Bmim]Cl/FeCl3 to acenaphthene being 4, the reaction temperature being 20 ℃, the reaction time being 4h and the solvent of the reaction system being PhNO2. Under those conditions, the yield of the 3,3’-biacenaphthene will be 48.71 % and selectivity of that will be 78.56 %. Further more, [bmim]Cl/FeCl3 has no pollution to environments and can be reused.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
Novel ionic liquids with dual acidity, of which the cation contains Brφnsted acidity and anions contain Lewis acidity were synthesized. These ionic liquids obtained were identified by NMR, FF-IR, SDT and FAB-MS. Thei...Novel ionic liquids with dual acidity, of which the cation contains Brφnsted acidity and anions contain Lewis acidity were synthesized. These ionic liquids obtained were identified by NMR, FF-IR, SDT and FAB-MS. Their acidities were determined by pyridine probe on IR spectrography.展开更多
Dry-spun Carbon Nanotube(CNT)fibers were surface-modified by atmospheric pressure oxygen plasma functionalization using a well controlled and continuous process.The fibers were characterized by scanning electron micro...Dry-spun Carbon Nanotube(CNT)fibers were surface-modified by atmospheric pressure oxygen plasma functionalization using a well controlled and continuous process.The fibers were characterized by scanning electron microscopy(SEM),Raman spectroscopy,and X-ray Photoelectron Spectroscopy(XPS).It was found from the conducted electrochemical measurements that the functionalized fibers showed a 132.8% increase in specific capacitance compared to non-functionalized fibers.Dye-adsorption test and the obtained Randles-Sevcik plot demonstrated that the oxygen plasma functionalized fibers exhibited increased surface area.It was further established by Brunauer-Emmett-Teller(BET)measurements that the surface area of the CNT fibers was increased from 168.22 m^2/g to 208.01 m^2/g after plasma functionalization.The pore size distribution of the fibers was also altered by this processing.The improved electrochemical data was attributed to enhanced wettability,increased surface area,and the presence of oxygen functional groups,which promoted the capacitance of the fibers.Fiber supercapacitors were fabricated from the oxygen plasma functionalized CNT fiber electrodes using different electrolyte systems.The devices with functionalized electrodes exhibited excellent cyclic stability(93.2% after 4000 cycles),flexibility,bendability,and good energy densities.At 0.5 m A/cm^2,the EMIMBF4 device revealed a specific capacitance,which is 27% and 65%greater than the specific capacitances of devices using EMIMTFSI and H2SO4 electrolytes,respectively.The practiced in this work plasma surface processing can be employed in other applications where fibers,yarns,ribbons,and sheets need to be chemically modified.展开更多
Ionic liquids(ILs)have shown excellent performance in the separation of binary azeotropes through extractive distillation[1].But the role of the ionic liquid in azeotropic system is not well understood.In this paper,C...Ionic liquids(ILs)have shown excellent performance in the separation of binary azeotropes through extractive distillation[1].But the role of the ionic liquid in azeotropic system is not well understood.In this paper,COSMO-RS model was applied to screen an appropriate IL to separate the binary azeotrope of ethyl acetate(EA)and ethanol and 1-octyl-3-methylimidazolium tetrafluoroborate([OMIM][BF4])was selected.The Quantum Mechanics(QM)calculations and molecular dynamics(MD)simulation are performed to study the interactions between the solvent molecules and[OMIM][BF4],in order to investigate the separation mechanism at the molecular level.The nature of the interactions is studied through the reduced density gradient(RDG)function and quantum theory of Atom in Molecule(QTAIM).Hydrogen bonds and van der Waals interactions are the key interactions in the complexes.The results of MD simulations indicate that the introduction of ILs has a prominent effect on the interaction between the solvent molecules,especially on reducing the number of hydrogen bonds among the solvent molecules.The radial distribution function(RDF)reveals that the interaction between the cation and solvent molecules will increase while the concentration of ILs increases.This paper provides important information for understanding the role of ILs in the separation of the azeotropic system,which is valuable to the development of new entrainers.展开更多
The Hartree-Fock and DFT/B3LYP methods have been employed to investigate the electronic structures of 1-ethyl-3-methyl-imidazolium cation (EMIM+), BF4^-, PF6^-, EMIM+BF4^-, and EMIM+-PF6^- using the Gaussian-94 s...The Hartree-Fock and DFT/B3LYP methods have been employed to investigate the electronic structures of 1-ethyl-3-methyl-imidazolium cation (EMIM+), BF4^-, PF6^-, EMIM+BF4^-, and EMIM+-PF6^- using the Gaussian-94 soft-package at 6-31+G(d,p) basis set level for hydrogen, carbon, nitrogen, boron, phosphorus, and fluorine atoms. Comparison of the electronic structures of the lowest energy of EMIM+- BF4^- and EMIM+-PF6^- pairs, and single EMIM+, BF4^- and PF6^- showed that the optimized EMIM+-BF4^- and EMIM+-PF6^- pair conformers were BF4^- and PF6^- outside the 5-ring plane between the ethyl group and the methyl group. The cohesion of C H. … F hydrogen bond between cation and anion is reinforced by charge assistance. The interaction energy between EMIM+ and PF6 is 328.8 kJ/mol at the B3LYP level and 326.6 kJ/mol at the Hartree-Fock level, whereas that between EMIM+ and BF4 is 353.5 kJ/mol at the B3LYP level and 350.5 kJ/mol at the Hartree-Fock level. The low energy interactions caused by bulky asymmetric EMIM+, and charge dispersion of cation and anion give rise to the low melting point of ionic liquid EMIM+-BF4^- and EMIM+-PF6^-. The two hydrogen bonding models of single hydrogen bond formation, and the hydrogen transfer between C2 in EMIM+ and F in BF4^- or PF6^- were principally depicted.展开更多
The batch reaction experiments have been made for the first time to investigate the effect of ionic structure on the reactivity and selectivity of the trioxane-forming reaction catalyzed by a Br?nsted-acidic ionic liq...The batch reaction experiments have been made for the first time to investigate the effect of ionic structure on the reactivity and selectivity of the trioxane-forming reaction catalyzed by a Br?nsted-acidic ionic liquid(IL).The ILs considered include 1-cyclohexyl-2-pyrrolidinonium trifluoromethanesulfonate([NCy P][TfO ]),1-cyclohexyl-2-pyrrolidinonium benzenesulfonate([NCyP ][BSA]),1-cyclohexyl-2-pyrrolidinonium p-toluenesulfonate([NCyP ][pTSA]),1-octyl-2-pyrrolidinonium 2,4-dinitrobenzenesulfonate([NOP][DNBSA]),1-octyl-2-pyrrolidinonium benzenesulfonate([NOP][BSA]),1-octyl-2-pyrrolidinonium methanesulfonate([NOP][MSA]),and 1-octyl-2-pyrrolidinonium trifluoromethanesulfonate([NOP][Tf O]).It is found that the yield of trioxane in the reaction solution correlates inversely with the Hammett acidity function H0 of the aqueous solution of the corresponding ILs.Variation of the cation structure from [NCyP ]+to [NOP]+exerts little influence on the yield and the selectivity of trioxane in the reaction solution.Using [TfO ]-or [DNBSA]-in place of [MSA]-or [BSA]-apparently increases the yield of trioxane,but only slightly increases the concentration of formic acid in the reaction solution.The continuous production experiments have been made to investigate the performance of [NOP][MSA],[NOP][DNBSA],[NCyP ][TfO ],and H2SO4 as an extraction distillation agent.Such effect of [NCyP ][TfO ] considerably overrides that of H2SO4.The yield and the selectivity of trioxane are both increased when [NCyP ][TfO ] is used instead of H2SO4 at a reaction time 5 h.展开更多
The geometries of reactant, product and transition state of the title reaction have been optimized by using density functional theory (DFT) at the B3LYP/6-31G(d,p) and B3LYP/6- 311++G(d,p) levels. The variations of th...The geometries of reactant, product and transition state of the title reaction have been optimized by using density functional theory (DFT) at the B3LYP/6-31G(d,p) and B3LYP/6- 311++G(d,p) levels. The variations of the bond parameters in the course of reaction were analyzed. The zero point energy corrections were performed by vibrational analysis. The equilibrium states and the transition state were verified according to the number of virtue frequency of geometry. The intrinsic reaction coordinates (IRC) were calculated from the transition state. The calculated results show that the double bond rearrangement of butene catalyzed by 1-butyl-3-methyl-imidazolium cation is a one-step reaction. The forward energy barrier of isomerization from 1-butene to 2- butene is about 193 kJ·mol-1 and the reverse energy barrier about 209 kJ·mol-1 at the B3LYP/6- 31G(d,p) level, which means that the reaction is easy to proceed at or above room temperature.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the Key Project of Shanghai Educational Committee(No.06ZZ82)
文摘Fischer indole cyclization of phenylhydrazine and various ketones using carboxyl-functionalized ionic liquid, 1-carboxymethyl- 3-methylimidazolium tetrafluoroborate (abbreviated as [crnmim] [BF4]) as catalyst was successfully performed. The yields of the target compounds were 80-92%, the purities were 96-98%. The catalyst could be recovered and reused for at least six times without significant loss in activity.
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 SOH-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financially supported by the National Natural Science Foundation of China(Nos.21673077,21473058,and 21273077)
文摘The phosphine-functionalized phosphonium-based ionic liquids(dppm-Q, dppe-Q, dppp-Q and dppb-Q) as the bi-functional ligands enable the efficient one-pot tandem hydroformylationeacetalization. It was found that, in dppm-Q, dppe-Q, dppp-Q and dppb-Q, the incorporated phosphino-fragments were responsible for Rh-catalyzed hydroformylation and the phosphoniums were in charge of the subsequent acetalization as the Lewis acid catalysts. Moreover, the diphosphonium-based ionic liquid of dppb-DQ could be applied as a co-solvent to immobilize the Rh/dppb-Q catalytic system with the advantages of the improved catalytic performance, the available catalyst recyclability, and the wide generality for the substrates.
基金financially supported by the Research and Development Program of the Ministry of Science and Technology of China (Grant No. 2014BAC28B01)the Jiangsu Key Laboratory of Anaerobic Biotechnology (Jiangnan University) Supported Research Project (No. JKLAB201703)
文摘An innovative approach to H2 S capture has been developed using several metal-based ionic liquids([Bmim]Cl·CuCl_2, [Bmim]Cl·FeCl_3, [Bmim]Cl·ZnCl_2, [Bmim]Br·CuCl_2, and [Bmim]Br·FeCl_3) immobilized on the sol-gel derived silica, which is superior to purely viscous ionic liquid with a crucial limit of high temperature, low mass transfer rate,and mass loss. The adsorbents were characterized by the Fourier transform infrared spectrometer, transmission electron microscope, N_2 adsorption/desorption, X-ray photoelectron spectroscopy, and thermal analysis techniques. The effects of the metal and halogen in IL, the loading amount of IL, and the adsorption temperature were studied by dynamic adsorption experiments at a gas flow rate of 100 mL/min. The H2 S adsorption results have showed that the optimal adsorbent and adsorption temperature are 5% [Bmim]Cl·CuCl_2/silica gel and 20—50 ℃, respectively. H_2 S can be captured and oxidized to elemental sulfur, and [Bmim]Cl·CuCl_2/silica gel can be readily regenerated by air. The excellent efficiency of H2 S removal may be attributed to the formation of nano-scaled and high-concentration [Bmim]Cl·CuCl_2 confined in silica gel, indicating that the immobilization of [Bmim]Cl·CuCl_2 on the sol-gel derived silica can be used for H2 S removal promisingly.
基金the Natural Science Foundation Project of CQ CSTC, 2010BB0201
文摘A series of functionalized ionic liquids (ILs) containing ester-group were synthesized and their tribological properties as lubricants for steel-steel contact were studied and compared with a non-functionalized ionic liquid and perfluoropolyethers (PFPE). The morphology and chemical composition of the worn scars were analyzed by scanning electron microscopy and X-ray photoelectron spectroscopy, respectively, and the possible lubrication mechanism of ILs was discussed. As a result, all ILs demonstrated a better lubricity and a much higher load-carrying capacity than PFPE used as lubricants for the steel-steel tribomates system. The functionalized ILs with ester-group showed slightly worse friction reducing ability than their nonfunctionalized counterparts at relatively lower loads owing to their higher viscosity, but then exhibited better antiwear ability because the ester group they contained had not only physical but also strong chemical reactions with the freshly exposed steel surface and formed chemical adsorption boundary films on the worn surface during friction process. Under high loads, some tribochemical reactions took place between the active elements, such as fluorine which were released from the ILs, and fresh metal surfaces of rubbing pairs to form the admixture reaction films, which were mainly composed of ferric fluoride mixed with ferric oxide, leading to lower friction coefficients and good wear resistance.
基金supported by the National Natural Science Foundation of China (21306007 and 21176020)Research Fund for the Doctoral Program of Higher Education of China (20130010120005)
文摘Room-temperature ionic liquids(ILs), which have excellent properties, such as high gas absorption abilities, extremely low volatility and tunable structures, are regarded as environmentally-friendly absorbents and widely used in SO_2 absorption and separation. As a result, a large number of ILs have been synthesized to capture SO_2 from flue gas or simulated gas, but a part of them just have physical interaction with SO_2 and can hardly absorb SO_2 when the content of SO_2 is very low. Hence, functional ILs, which can chemically absorb a large amount of SO_2 with low contents, have been designed and synthesized for SO_2 capture. Up to now, many kinds of functional ILs were investigated for SO_2 absorption from flue gas. In this review, the functional ILs are classified into guanidinium based ILs, hydroxyl ammonium based ILs, imidazolium/pyridinium based ILs, quaternary ammonium based ILs, phosphonium based ILs, and other kinds of ILs according to their cations. The capacities of SO_2 absorption in these ILs, the mechanism of the absorption, and the ways to enhance the absorption are briefly introduced. The prospect of functional ILs for their application in SO_2 removal is presented. The present problems and the further studies are also discussed.
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National Natural Science Foundation of China (No. 20207003)
文摘To obtain new functional aromatic polymer material, 3,3’-biacenaphthene, which is used as macromolecule intermediate of function aromatic polymer material, was synthesized through the coupling reaction of acenaphthene catalyzing by ionic liquid ([bmim]Cl/FeCl3) at mild reaction condition. Pure 3,3’-biacenaphthene was obtained by recrystalling and column chromatography from the reaction mixture and was determined by GC/MS, 1HNMR and FTIR analysis. The influence of various reaction conditions on the yield of 3,3’-biacenaphthene were studied by GC analysis. The result shows that the optimum synthesis conditions of the coupling reaction are as following: the molar ratio of FeCl3 to [Bmim]Cl being 3, the mole ratio of FeCl3 in [Bmim]Cl/FeCl3 to acenaphthene being 4, the reaction temperature being 20 ℃, the reaction time being 4h and the solvent of the reaction system being PhNO2. Under those conditions, the yield of the 3,3’-biacenaphthene will be 48.71 % and selectivity of that will be 78.56 %. Further more, [bmim]Cl/FeCl3 has no pollution to environments and can be reused.
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the‘973’Program of the Chinese Ministry of Science and Technology(G-2000048002).
文摘Novel ionic liquids with dual acidity, of which the cation contains Brφnsted acidity and anions contain Lewis acidity were synthesized. These ionic liquids obtained were identified by NMR, FF-IR, SDT and FAB-MS. Their acidities were determined by pyridine probe on IR spectrography.
基金funded by a NASA Grant NNX13AF46Apartly by the National Institute for Occupational Safety and Health through the UC Pilot Research Project Training Program ERC Grant #T42OH008432
文摘Dry-spun Carbon Nanotube(CNT)fibers were surface-modified by atmospheric pressure oxygen plasma functionalization using a well controlled and continuous process.The fibers were characterized by scanning electron microscopy(SEM),Raman spectroscopy,and X-ray Photoelectron Spectroscopy(XPS).It was found from the conducted electrochemical measurements that the functionalized fibers showed a 132.8% increase in specific capacitance compared to non-functionalized fibers.Dye-adsorption test and the obtained Randles-Sevcik plot demonstrated that the oxygen plasma functionalized fibers exhibited increased surface area.It was further established by Brunauer-Emmett-Teller(BET)measurements that the surface area of the CNT fibers was increased from 168.22 m^2/g to 208.01 m^2/g after plasma functionalization.The pore size distribution of the fibers was also altered by this processing.The improved electrochemical data was attributed to enhanced wettability,increased surface area,and the presence of oxygen functional groups,which promoted the capacitance of the fibers.Fiber supercapacitors were fabricated from the oxygen plasma functionalized CNT fiber electrodes using different electrolyte systems.The devices with functionalized electrodes exhibited excellent cyclic stability(93.2% after 4000 cycles),flexibility,bendability,and good energy densities.At 0.5 m A/cm^2,the EMIMBF4 device revealed a specific capacitance,which is 27% and 65%greater than the specific capacitances of devices using EMIMTFSI and H2SO4 electrolytes,respectively.The practiced in this work plasma surface processing can be employed in other applications where fibers,yarns,ribbons,and sheets need to be chemically modified.
基金support from the Program for the National Key R&D Program of China(2018YFB0604900)the National Natural Science Foundation of China(No.21878219)+1 种基金the financial support by the Natural Sciences and Engineering Research Council(NSERC)of Canada(RGPIN-4903-2014)China Scholarship Council(CSC)for supporting his doctoral study at McMaster University(No.201500090106)
文摘Ionic liquids(ILs)have shown excellent performance in the separation of binary azeotropes through extractive distillation[1].But the role of the ionic liquid in azeotropic system is not well understood.In this paper,COSMO-RS model was applied to screen an appropriate IL to separate the binary azeotrope of ethyl acetate(EA)and ethanol and 1-octyl-3-methylimidazolium tetrafluoroborate([OMIM][BF4])was selected.The Quantum Mechanics(QM)calculations and molecular dynamics(MD)simulation are performed to study the interactions between the solvent molecules and[OMIM][BF4],in order to investigate the separation mechanism at the molecular level.The nature of the interactions is studied through the reduced density gradient(RDG)function and quantum theory of Atom in Molecule(QTAIM).Hydrogen bonds and van der Waals interactions are the key interactions in the complexes.The results of MD simulations indicate that the introduction of ILs has a prominent effect on the interaction between the solvent molecules,especially on reducing the number of hydrogen bonds among the solvent molecules.The radial distribution function(RDF)reveals that the interaction between the cation and solvent molecules will increase while the concentration of ILs increases.This paper provides important information for understanding the role of ILs in the separation of the azeotropic system,which is valuable to the development of new entrainers.
文摘The Hartree-Fock and DFT/B3LYP methods have been employed to investigate the electronic structures of 1-ethyl-3-methyl-imidazolium cation (EMIM+), BF4^-, PF6^-, EMIM+BF4^-, and EMIM+-PF6^- using the Gaussian-94 soft-package at 6-31+G(d,p) basis set level for hydrogen, carbon, nitrogen, boron, phosphorus, and fluorine atoms. Comparison of the electronic structures of the lowest energy of EMIM+- BF4^- and EMIM+-PF6^- pairs, and single EMIM+, BF4^- and PF6^- showed that the optimized EMIM+-BF4^- and EMIM+-PF6^- pair conformers were BF4^- and PF6^- outside the 5-ring plane between the ethyl group and the methyl group. The cohesion of C H. … F hydrogen bond between cation and anion is reinforced by charge assistance. The interaction energy between EMIM+ and PF6 is 328.8 kJ/mol at the B3LYP level and 326.6 kJ/mol at the Hartree-Fock level, whereas that between EMIM+ and BF4 is 353.5 kJ/mol at the B3LYP level and 350.5 kJ/mol at the Hartree-Fock level. The low energy interactions caused by bulky asymmetric EMIM+, and charge dispersion of cation and anion give rise to the low melting point of ionic liquid EMIM+-BF4^- and EMIM+-PF6^-. The two hydrogen bonding models of single hydrogen bond formation, and the hydrogen transfer between C2 in EMIM+ and F in BF4^- or PF6^- were principally depicted.
基金Supported by the National Natural Science Foundation of China(21576285,21276271)
文摘The batch reaction experiments have been made for the first time to investigate the effect of ionic structure on the reactivity and selectivity of the trioxane-forming reaction catalyzed by a Br?nsted-acidic ionic liquid(IL).The ILs considered include 1-cyclohexyl-2-pyrrolidinonium trifluoromethanesulfonate([NCy P][TfO ]),1-cyclohexyl-2-pyrrolidinonium benzenesulfonate([NCyP ][BSA]),1-cyclohexyl-2-pyrrolidinonium p-toluenesulfonate([NCyP ][pTSA]),1-octyl-2-pyrrolidinonium 2,4-dinitrobenzenesulfonate([NOP][DNBSA]),1-octyl-2-pyrrolidinonium benzenesulfonate([NOP][BSA]),1-octyl-2-pyrrolidinonium methanesulfonate([NOP][MSA]),and 1-octyl-2-pyrrolidinonium trifluoromethanesulfonate([NOP][Tf O]).It is found that the yield of trioxane in the reaction solution correlates inversely with the Hammett acidity function H0 of the aqueous solution of the corresponding ILs.Variation of the cation structure from [NCyP ]+to [NOP]+exerts little influence on the yield and the selectivity of trioxane in the reaction solution.Using [TfO ]-or [DNBSA]-in place of [MSA]-or [BSA]-apparently increases the yield of trioxane,but only slightly increases the concentration of formic acid in the reaction solution.The continuous production experiments have been made to investigate the performance of [NOP][MSA],[NOP][DNBSA],[NCyP ][TfO ],and H2SO4 as an extraction distillation agent.Such effect of [NCyP ][TfO ] considerably overrides that of H2SO4.The yield and the selectivity of trioxane are both increased when [NCyP ][TfO ] is used instead of H2SO4 at a reaction time 5 h.
基金This work was supported by the National Natural Science Key Foundation of China (20490209) and Young Teacher Foundation of Beijing Chemical Technology University (QN0308)
文摘The geometries of reactant, product and transition state of the title reaction have been optimized by using density functional theory (DFT) at the B3LYP/6-31G(d,p) and B3LYP/6- 311++G(d,p) levels. The variations of the bond parameters in the course of reaction were analyzed. The zero point energy corrections were performed by vibrational analysis. The equilibrium states and the transition state were verified according to the number of virtue frequency of geometry. The intrinsic reaction coordinates (IRC) were calculated from the transition state. The calculated results show that the double bond rearrangement of butene catalyzed by 1-butyl-3-methyl-imidazolium cation is a one-step reaction. The forward energy barrier of isomerization from 1-butene to 2- butene is about 193 kJ·mol-1 and the reverse energy barrier about 209 kJ·mol-1 at the B3LYP/6- 31G(d,p) level, which means that the reaction is easy to proceed at or above room temperature.