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
FeCl3-based ionic liquid [Bmim]Br/FeCl3 with lower viscosity was synthesized and its structure was character-ized with FT-IR spectroscopy. The denitrogenation performance of the ionic liquid was investigated using the...FeCl3-based ionic liquid [Bmim]Br/FeCl3 with lower viscosity was synthesized and its structure was character-ized with FT-IR spectroscopy. The denitrogenation performance of the ionic liquid was investigated using the Fushun shale diesel fraction with high nitrogen content. Experimental results showed that the ionic liquid presented good denitrogenation performance and the basic N and total N removal efficiency can reach 95.29% and 89.77% under conditions covering a tem-perature of 30 ℃, an IL/oil mass ratio of 1:1, an extraction time of 30 min, and a settling time of 2 h. Correspondingly, the basic N and total N contents in shale diesel fraction dropped from the original 5454 μg/g and 9832 μg/g to 257 μg/g and 1006 μg/g, respectively. In addition, the basic-N removal efficiency can still reach 60% at an IL/oil mass ratio of 1:7 during four recycles of the ionic liquid.展开更多
The phase diagram of InCl3-MBIC was constructed by DSC method. A clear, colorless and mobile ionic liquid was obtained and liquid down to 258 K. Both Raman scattering and ab initio calculations indicate that InCl4- ...The phase diagram of InCl3-MBIC was constructed by DSC method. A clear, colorless and mobile ionic liquid was obtained and liquid down to 258 K. Both Raman scattering and ab initio calculations indicate that InCl4- is the predominant anion.展开更多
The Hartree-Fock method has been employed to investigate the electronic structures of EMIM^+(1-ethyl-3-methyl-imidazolium^+), CuCl2^-, Cu2Cl3^-, CuCl3^2-, EMIM+^-CuCl2^-, EMIM^+-Cu2Cl3^-, and EMIM^+-CuCl3^2- pa...The Hartree-Fock method has been employed to investigate the electronic structures of EMIM^+(1-ethyl-3-methyl-imidazolium^+), CuCl2^-, Cu2Cl3^-, CuCl3^2-, EMIM+^-CuCl2^-, EMIM^+-Cu2Cl3^-, and EMIM^+-CuCl3^2- pairs. Full optimization and frequency analyses of EMIM^+, CuCl2^-, Cu2Cl3^-, CuC13^-, eight initial EMIM^+-CuCl2^-, six EMIM^+-Cu2Cl3^-, and four EMIM^+-CuCl3^2- geometries have been carried out using Gaussian-94 soft-package at 6-31+G(d,p) basis set level for hydrogen, carbon, nitrogen, chlorine atoms and Hay-Wadt effective core potential for copper atom. The electronic structures of lowest energy of EMIM^+-CuCl2^-, EMIM+-Cu2Cl3^-, EMIM^+-CuCl3^2-, single EMIM^+, CuCl2^-, Cu2Cl3^-, and CuCl3^2- have been comparatively studied. The calculated results showed that EMIM^+-CuCl2^- pair conformer of lowest energy was five ring parallel to Cl-Cu-Cl with 3.2A distance, EMIM^+-CuCl3^2- pair conformer of lowest energy was five ring parallel to CuCl3^2-plane with 3.4A distance, and the optimized EMIM^+-Cu2Cl3^- pair conformer of lowest energy was five ring perpendicular to Cl-Cu-Cl-Cu-Cl plane with 3.0A distance between the terminal Cl atoms and the 5-ring of EMIM^+. The cohesion between cations and anions is brought about by C-H. C1 hydrogen bonds that are reinforced by charge assistance. The frequency analyses suggested that all stationary points are minimum because of no appearing of imaginary frequency. The assigned frequencies were in agreement with the experimental report. The low energy of interaction because of the bulkyasymmetry of EMIM+ and the charge dispersion of cation and anion leads to the low melting point of the ionic liquids, EMIM^+-CuCl2^-, EMIM^+-Cu2Cl3^-, and EMIM^+-CuCl3^2-. The interaction energy of EMIM^+-CuCl2^-, EMIM^+-Cu2Cl3^-, and EMIM^+-CuCl3^2- is 309.0 kJ/mol, 316.8 kJ/mol, and 320.2 kJ/mol, respectively. The relationship of interaction energy via distance between cations and anions was also investigated by single point energy scan.展开更多
Several 1-vinyl-3-alkylimidazolium halogens [VRIM]X, which are functional materials with ethylenic bonds, were synthesized using the microwave-assisted synthesis method. Fourier transform infrared spectroscopy and 1H ...Several 1-vinyl-3-alkylimidazolium halogens [VRIM]X, which are functional materials with ethylenic bonds, were synthesized using the microwave-assisted synthesis method. Fourier transform infrared spectroscopy and 1H nuclear magnetic resonance spectroscopy were carded out to analyze the resultant structures. The electrochemical properties and solubility of [VRIM]Br were investigated and discussed in detail. The temperature dependence of pure [VRIM]Br over a wide temperature range of 298.15-323.15 K fitted the Arrhanius equation well. At certain low concentrations, the electrical conductivity of the [VRIM]Br solution significantly increased with increasing solution concentration. The electrical conductivities of the [VRIM]Br observed in water, methanol, and ethanol showed the trend σwater〉 σmethanol 〉σethanol Conductometry showed that the critical miceUe concentrations of the bromines in water, methanol, and ethanol were 6.8-6.9 × 10-6, 1.4-1.5 × 10-5, and 1.9-2.0×10-5 mol.L-1, respectively; these results indicate that [VRIM]Br is an excellent surfactant. The solubility of [VRIM]X in common solvents was determined at 293.15 K, and results indicated that a decrease in solubility could be observed with decreasing dielectric constant of the solvent, elongation of the alkyl chain of the cation, and increasing anion size. Solubility parameters were also determined according to the Hildebrand-Scoff equation.展开更多
bmim]Cl/FeCl3 ionic liquids (where bmim = 1-butyl-3-methylimidazolium) were characterized by XPS (X-ray photoelectron spectroscopy), FT-IR (Fourier transform infrared spectroscopy), Raman and NMR (nuclear magnetic r...bmim]Cl/FeCl3 ionic liquids (where bmim = 1-butyl-3-methylimidazolium) were characterized by XPS (X-ray photoelectron spectroscopy), FT-IR (Fourier transform infrared spectroscopy), Raman and NMR (nuclear magnetic resonance) spectra. The results show that Fe2Cl7 and FeCl4 ions are the principal anions in acidic ionic liquids, - - whose concentrations change with the content of FeCl3 and an equilibrium exists between them. An isosbestic point existing in FT-IR spectra indicates that an interaction involving at least two species occurs and their concentrations vary with acidity. Chemical shifts of the hydrogen located in the cations of ionic liquids are sensitive to the composition of ionic liquids. The change in chemical shifts may be explained in terms of anion-cation interactions. The chemical shifts of 2-H are affected by metal halides, which shift downfield and the 2-H is more deshielded with the increase in metal halides.展开更多
This paper reports the ab initio and Density Functional Theory (DFT) studies on the structure of the ionic liquid 1-ethyl-3-methylimidazolium hexafluorophosphate ([EMIM]+[PF6]-). Hartree-Fock (HF) and DFT(B3LYP) metho...This paper reports the ab initio and Density Functional Theory (DFT) studies on the structure of the ionic liquid 1-ethyl-3-methylimidazolium hexafluorophosphate ([EMIM]+[PF6]-). Hartree-Fock (HF) and DFT(B3LYP) methods are respectively used to obtain the stable structure of the gas phase ion pair at the 6-311++G(d, p) basis set level. The theoretical IR spectra of [EMIM]+[PF6]- were obtained from the calculated vibrational frequencies and intensities. The changes of atomic charge population have been investigated using Natural Bond Orbital (NBO) analysis. The computational results show that there may exist hydrogen bonds between the cation and the anion. After ZPE and BSSE corrections, the interaction energy between the cation and the anion is –314.44 kJ?mol-1.展开更多
Silica-grafted N-propyl-imidazolium hydrogen sulfate ([Sipim]HSO4) is employed as a recyclable heterogeneous ionic liquid catalyst for the synthesis of 3,4-dihydropyrano[c]-chromenes by the reaction of aromatic aldehy...Silica-grafted N-propyl-imidazolium hydrogen sulfate ([Sipim]HSO4) is employed as a recyclable heterogeneous ionic liquid catalyst for the synthesis of 3,4-dihydropyrano[c]-chromenes by the reaction of aromatic aldehydes, malononitrile and 4-hydroxycoumarin at 100°C under solvent-free conditions. Also, heterogeneous ionic liquid catalyst was used for the synthesis of pyrano[2,3-c]-pyrazoles by the reaction of aromatic aldehydes, malononitrile and 3-methyl-l-phenyl-5-pyrazolone at 110°C under solvent-free conditions. The heterogeneous ionic liquid showed much the same efficiency when used in consecutive reaction runs.展开更多
The random copolymer poly (1, 3-pentadiene-co-styrene) formed through cationic copolymerization using the ~ethylamine hydrochloride and hydrous aluminium chloride (Et3NHCl-AlCl3) room temperature ionic liquid as i...The random copolymer poly (1, 3-pentadiene-co-styrene) formed through cationic copolymerization using the ~ethylamine hydrochloride and hydrous aluminium chloride (Et3NHCl-AlCl3) room temperature ionic liquid as initiating agent in toluene was analyzed using IR spectra in conjunction with gel permeation chromatography (GPC). The room temperature ionic liquid was found to have high initiatic activity for copolymerization.展开更多
A highly selective synthesis of 2,6-dimethylnaphthanlene(2,6-DMN) by transalkylation between 2-methylnaphthanlene(2-MN) and 1,2,4,5-tetramethylbenzene(TeMB) was performed with 1-alkyl-3-methylimidazo- lium alumi...A highly selective synthesis of 2,6-dimethylnaphthanlene(2,6-DMN) by transalkylation between 2-methylnaphthanlene(2-MN) and 1,2,4,5-tetramethylbenzene(TeMB) was performed with 1-alkyl-3-methylimidazo- lium aluminum chloride([Cnmim]Cl-AlCl3) ionic liquids(ILs) as catalysts. The influences of the alkyl group as the organic cation, the acidic strength of [C4mim]Cl-AlCl3 ILs as well as the reaction conditions on the catalytic performance were investigated. [C4mim]Cl-AlCl3 ILs[x(AlCl3)=71%] exhibited high activity and selectivity toward 2,6-DMN. The selectivity to 2,6-DMN and the 2,6-DMN/2,7-DMN ratio reached up to 68.2% and 3.7:1, respectively. The UV-Vis spectrum of TeMB treated by different ILs shows that the protonated degree of TeMB dependeds on the acidity strength of ILs, which has a significant impact on the reaction results. The high protonated degree of TeMB is advantageous to enhancing the conversion of transalkylation and the large stereo-hindrance effect of TeMB is favorable to improving the selecivity to 2,6-DMN.展开更多
Helicity-dependent photocurrent(HDPC)of the surface states in a high-quality topological insulator(Bi_(0.7)Sb_(0.3))_(2)Te_(3)nanoplate grown by chemical vapor deposition(CVD)is investigated.By investigating the angle...Helicity-dependent photocurrent(HDPC)of the surface states in a high-quality topological insulator(Bi_(0.7)Sb_(0.3))_(2)Te_(3)nanoplate grown by chemical vapor deposition(CVD)is investigated.By investigating the angle-dependent HDPC,it is found that the HDPC is mainly contributed by the circular photogalvanic effect(CPGE)current when the incident plane is perpendicular to the connection of the two contacts,whereas the circular photon drag effect(CPDE)dominates the HDPC when the incident plane is parallel to the connection of the two contacts.In addition,the CPGE of the(Bi_(0.7)Sb_(0.3))_(2)Te_(3)nanoplate is regulated by temperature,light power,excitation wavelength,the source–drain and ionic liquid top-gate voltages,and the regulation mechanisms are discussed.It is demonstrated that(Bi_(0.7)Sb_(0.3))_(2)Te_(3)nanoplates may provide a good platform for novel opto-spintronics devices.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
In this paper, the effect of ionic liquids on the CaCO3 crystal growth has been studied for the first time. The obtained CaCO3 crystals were charactered by the X-ray diffraction and scanning electron micrographs. The ...In this paper, the effect of ionic liquids on the CaCO3 crystal growth has been studied for the first time. The obtained CaCO3 crystals were charactered by the X-ray diffraction and scanning electron micrographs. The results showed that the control ability of ionic liquids for CaCO3 crystals growth was dependent on the counter anion very much.展开更多
Specific fluorophore was introduced into ionic liquid based on its tunability,thus a kind of novel fluorescent ionic liquid probe[P66614][HQS]was designed,synthesized and characterized.Compared with non-fluorescent HQ...Specific fluorophore was introduced into ionic liquid based on its tunability,thus a kind of novel fluorescent ionic liquid probe[P66614][HQS]was designed,synthesized and characterized.Compared with non-fluorescent HQS,ionic liquid[P66614][HQS]emitted a certain amount of fluorescence,which could be attributed to the well-delocalized frontier orbitals and its charge transfer character,as demonstrated by quantum chemical calculation.Considering the interaction of[P66614][HQS]with metal ions,the application for detecting specific substance as a chemical sensor,such as Al3+was investigated.Compared with the traditional probe HQS,significant improvements in Al^3+detecting was achieved by[P66614][HQS]with stronger binding ability,better sensitivity and selectivity.The better performance of[P66614][HQS]was contributed to the changed charge distribution,leading to the stronger binding interaction.We believe that this new fluorescent ionic liquid exhibited unique properties in detecting Al^3+in aqueous solution,which would broaden the application of ionic liquids.展开更多
The main advantages of the use of ionic liquids in enhanced oil recovery are their tunability and stability in harsh environmental conditions. In this work, a comprehensive review of ionic liquids proposed to improve ...The main advantages of the use of ionic liquids in enhanced oil recovery are their tunability and stability in harsh environmental conditions. In this work, a comprehensive review of ionic liquids proposed to improve current chemical oil recovery methods has been presented, focusing on core flooding experiments. With an almost infinite number of possible ionic liquids, the amount of experiments carried out up to now has been very limited. However, results are promising, with additional recovery after secondary flooding of up to 32% of the original oil in place. Most formulations with ionic liquids have been proposed for sandstone reservoirs, the number of studies with carbonate cores being very scarce. The possibilities of a new room temperature surface active ionic liquid, 1-decyl-3-methylimidazolium triflate,for this application were analyzed. It was shown that it is able to drastically reduce the water/oil interfacial tension. An optimized formulation was proposed for carbonate reservoirs. After secondary flooding with brine, an additional recovery of 10.5% of original oil in place was achieved at room conditions. A combination of the proposed method followed by a polymer flooding step with polyacrylamide led to a lesser but still significant recovery, reducing the costs associated to the ionic liquid.展开更多
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financial support from the Doctoral Funds of Liaoning Provincial Natural Science Foundation (201601323)
文摘FeCl3-based ionic liquid [Bmim]Br/FeCl3 with lower viscosity was synthesized and its structure was character-ized with FT-IR spectroscopy. The denitrogenation performance of the ionic liquid was investigated using the Fushun shale diesel fraction with high nitrogen content. Experimental results showed that the ionic liquid presented good denitrogenation performance and the basic N and total N removal efficiency can reach 95.29% and 89.77% under conditions covering a tem-perature of 30 ℃, an IL/oil mass ratio of 1:1, an extraction time of 30 min, and a settling time of 2 h. Correspondingly, the basic N and total N contents in shale diesel fraction dropped from the original 5454 μg/g and 9832 μg/g to 257 μg/g and 1006 μg/g, respectively. In addition, the basic-N removal efficiency can still reach 60% at an IL/oil mass ratio of 1:7 during four recycles of the ionic liquid.
基金supportcd by NSFC(20041005).by NSF of Liaoning provincc(20011O2O35);by Education Burcau of Liaoning prox,incc.
文摘The phase diagram of InCl3-MBIC was constructed by DSC method. A clear, colorless and mobile ionic liquid was obtained and liquid down to 258 K. Both Raman scattering and ab initio calculations indicate that InCl4- is the predominant anion.
文摘The Hartree-Fock method has been employed to investigate the electronic structures of EMIM^+(1-ethyl-3-methyl-imidazolium^+), CuCl2^-, Cu2Cl3^-, CuCl3^2-, EMIM+^-CuCl2^-, EMIM^+-Cu2Cl3^-, and EMIM^+-CuCl3^2- pairs. Full optimization and frequency analyses of EMIM^+, CuCl2^-, Cu2Cl3^-, CuC13^-, eight initial EMIM^+-CuCl2^-, six EMIM^+-Cu2Cl3^-, and four EMIM^+-CuCl3^2- geometries have been carried out using Gaussian-94 soft-package at 6-31+G(d,p) basis set level for hydrogen, carbon, nitrogen, chlorine atoms and Hay-Wadt effective core potential for copper atom. The electronic structures of lowest energy of EMIM^+-CuCl2^-, EMIM+-Cu2Cl3^-, EMIM^+-CuCl3^2-, single EMIM^+, CuCl2^-, Cu2Cl3^-, and CuCl3^2- have been comparatively studied. The calculated results showed that EMIM^+-CuCl2^- pair conformer of lowest energy was five ring parallel to Cl-Cu-Cl with 3.2A distance, EMIM^+-CuCl3^2- pair conformer of lowest energy was five ring parallel to CuCl3^2-plane with 3.4A distance, and the optimized EMIM^+-Cu2Cl3^- pair conformer of lowest energy was five ring perpendicular to Cl-Cu-Cl-Cu-Cl plane with 3.0A distance between the terminal Cl atoms and the 5-ring of EMIM^+. The cohesion between cations and anions is brought about by C-H. C1 hydrogen bonds that are reinforced by charge assistance. The frequency analyses suggested that all stationary points are minimum because of no appearing of imaginary frequency. The assigned frequencies were in agreement with the experimental report. The low energy of interaction because of the bulkyasymmetry of EMIM+ and the charge dispersion of cation and anion leads to the low melting point of the ionic liquids, EMIM^+-CuCl2^-, EMIM^+-Cu2Cl3^-, and EMIM^+-CuCl3^2-. The interaction energy of EMIM^+-CuCl2^-, EMIM^+-Cu2Cl3^-, and EMIM^+-CuCl3^2- is 309.0 kJ/mol, 316.8 kJ/mol, and 320.2 kJ/mol, respectively. The relationship of interaction energy via distance between cations and anions was also investigated by single point energy scan.
基金Funded by the Special Funds of the National Natural Science Foundation of China(No.21174111)
文摘Several 1-vinyl-3-alkylimidazolium halogens [VRIM]X, which are functional materials with ethylenic bonds, were synthesized using the microwave-assisted synthesis method. Fourier transform infrared spectroscopy and 1H nuclear magnetic resonance spectroscopy were carded out to analyze the resultant structures. The electrochemical properties and solubility of [VRIM]Br were investigated and discussed in detail. The temperature dependence of pure [VRIM]Br over a wide temperature range of 298.15-323.15 K fitted the Arrhanius equation well. At certain low concentrations, the electrical conductivity of the [VRIM]Br solution significantly increased with increasing solution concentration. The electrical conductivities of the [VRIM]Br observed in water, methanol, and ethanol showed the trend σwater〉 σmethanol 〉σethanol Conductometry showed that the critical miceUe concentrations of the bromines in water, methanol, and ethanol were 6.8-6.9 × 10-6, 1.4-1.5 × 10-5, and 1.9-2.0×10-5 mol.L-1, respectively; these results indicate that [VRIM]Br is an excellent surfactant. The solubility of [VRIM]X in common solvents was determined at 293.15 K, and results indicated that a decrease in solubility could be observed with decreasing dielectric constant of the solvent, elongation of the alkyl chain of the cation, and increasing anion size. Solubility parameters were also determined according to the Hildebrand-Scoff equation.
文摘bmim]Cl/FeCl3 ionic liquids (where bmim = 1-butyl-3-methylimidazolium) were characterized by XPS (X-ray photoelectron spectroscopy), FT-IR (Fourier transform infrared spectroscopy), Raman and NMR (nuclear magnetic resonance) spectra. The results show that Fe2Cl7 and FeCl4 ions are the principal anions in acidic ionic liquids, - - whose concentrations change with the content of FeCl3 and an equilibrium exists between them. An isosbestic point existing in FT-IR spectra indicates that an interaction involving at least two species occurs and their concentrations vary with acidity. Chemical shifts of the hydrogen located in the cations of ionic liquids are sensitive to the composition of ionic liquids. The change in chemical shifts may be explained in terms of anion-cation interactions. The chemical shifts of 2-H are affected by metal halides, which shift downfield and the 2-H is more deshielded with the increase in metal halides.
基金This work was supported by the National Natural Science Key Foundation of China (20490209) and Young Teacher Foundation of Beijing University of Chemical Technology (QN0308)
文摘This paper reports the ab initio and Density Functional Theory (DFT) studies on the structure of the ionic liquid 1-ethyl-3-methylimidazolium hexafluorophosphate ([EMIM]+[PF6]-). Hartree-Fock (HF) and DFT(B3LYP) methods are respectively used to obtain the stable structure of the gas phase ion pair at the 6-311++G(d, p) basis set level. The theoretical IR spectra of [EMIM]+[PF6]- were obtained from the calculated vibrational frequencies and intensities. The changes of atomic charge population have been investigated using Natural Bond Orbital (NBO) analysis. The computational results show that there may exist hydrogen bonds between the cation and the anion. After ZPE and BSSE corrections, the interaction energy between the cation and the anion is –314.44 kJ?mol-1.
文摘Silica-grafted N-propyl-imidazolium hydrogen sulfate ([Sipim]HSO4) is employed as a recyclable heterogeneous ionic liquid catalyst for the synthesis of 3,4-dihydropyrano[c]-chromenes by the reaction of aromatic aldehydes, malononitrile and 4-hydroxycoumarin at 100°C under solvent-free conditions. Also, heterogeneous ionic liquid catalyst was used for the synthesis of pyrano[2,3-c]-pyrazoles by the reaction of aromatic aldehydes, malononitrile and 3-methyl-l-phenyl-5-pyrazolone at 110°C under solvent-free conditions. The heterogeneous ionic liquid showed much the same efficiency when used in consecutive reaction runs.
基金the National Natural Science Foundation of China(No.20772025)the Program for Science & Technology Innovation Talents in Universities of Henan Province(No.2008HASTIT006)the Natural Science Foundation of Department of Education of Henan Province(No.2008A150013).
文摘The random copolymer poly (1, 3-pentadiene-co-styrene) formed through cationic copolymerization using the ~ethylamine hydrochloride and hydrous aluminium chloride (Et3NHCl-AlCl3) room temperature ionic liquid as initiating agent in toluene was analyzed using IR spectra in conjunction with gel permeation chromatography (GPC). The room temperature ionic liquid was found to have high initiatic activity for copolymerization.
基金Supported by the National Natural Science Foundation of China(No.21076065)the Natural Science Foundation of Heilongjiang Province of China(No.ZD200820-02)the Science&Technology Research Foundation of Education Bureau of Heilongjiang Province,China(No.11531266)
文摘A highly selective synthesis of 2,6-dimethylnaphthanlene(2,6-DMN) by transalkylation between 2-methylnaphthanlene(2-MN) and 1,2,4,5-tetramethylbenzene(TeMB) was performed with 1-alkyl-3-methylimidazo- lium aluminum chloride([Cnmim]Cl-AlCl3) ionic liquids(ILs) as catalysts. The influences of the alkyl group as the organic cation, the acidic strength of [C4mim]Cl-AlCl3 ILs as well as the reaction conditions on the catalytic performance were investigated. [C4mim]Cl-AlCl3 ILs[x(AlCl3)=71%] exhibited high activity and selectivity toward 2,6-DMN. The selectivity to 2,6-DMN and the 2,6-DMN/2,7-DMN ratio reached up to 68.2% and 3.7:1, respectively. The UV-Vis spectrum of TeMB treated by different ILs shows that the protonated degree of TeMB dependeds on the acidity strength of ILs, which has a significant impact on the reaction results. The high protonated degree of TeMB is advantageous to enhancing the conversion of transalkylation and the large stereo-hindrance effect of TeMB is favorable to improving the selecivity to 2,6-DMN.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.62074036,61674038,and 11574302)the Foreign Cooperation Project of Fujian Province,China(Grant No.2023I0005)+2 种基金the Open Research Fund Program of the State Key Laboratory of Low-Dimensional Quantum Physics(Grant No.KF202108)the National Key Research and Development Program of China(Grant No.2016YFB0402303)the Foundation of Fujian Provincial Department of Industry and Information Technology of China(Grant No.82318075)。
文摘Helicity-dependent photocurrent(HDPC)of the surface states in a high-quality topological insulator(Bi_(0.7)Sb_(0.3))_(2)Te_(3)nanoplate grown by chemical vapor deposition(CVD)is investigated.By investigating the angle-dependent HDPC,it is found that the HDPC is mainly contributed by the circular photogalvanic effect(CPGE)current when the incident plane is perpendicular to the connection of the two contacts,whereas the circular photon drag effect(CPDE)dominates the HDPC when the incident plane is parallel to the connection of the two contacts.In addition,the CPGE of the(Bi_(0.7)Sb_(0.3))_(2)Te_(3)nanoplate is regulated by temperature,light power,excitation wavelength,the source–drain and ionic liquid top-gate voltages,and the regulation mechanisms are discussed.It is demonstrated that(Bi_(0.7)Sb_(0.3))_(2)Te_(3)nanoplates may provide a good platform for novel opto-spintronics devices.
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.
文摘In this paper, the effect of ionic liquids on the CaCO3 crystal growth has been studied for the first time. The obtained CaCO3 crystals were charactered by the X-ray diffraction and scanning electron micrographs. The results showed that the control ability of ionic liquids for CaCO3 crystals growth was dependent on the counter anion very much.
基金We acknowledge the support of the National Key Basic Research Program of China(2015CB251401)the Natural Science Foundation of China(21776239)+1 种基金Zhejiang Provincial Natural Science Foundation of China(LZ17B060001)the Fundamental Research Funds of the Central Universities,the instrument support of professor Peng Xiaogang,professor Jin Yizheng and associate professor Qin Haiyan.
文摘Specific fluorophore was introduced into ionic liquid based on its tunability,thus a kind of novel fluorescent ionic liquid probe[P66614][HQS]was designed,synthesized and characterized.Compared with non-fluorescent HQS,ionic liquid[P66614][HQS]emitted a certain amount of fluorescence,which could be attributed to the well-delocalized frontier orbitals and its charge transfer character,as demonstrated by quantum chemical calculation.Considering the interaction of[P66614][HQS]with metal ions,the application for detecting specific substance as a chemical sensor,such as Al3+was investigated.Compared with the traditional probe HQS,significant improvements in Al^3+detecting was achieved by[P66614][HQS]with stronger binding ability,better sensitivity and selectivity.The better performance of[P66614][HQS]was contributed to the changed charge distribution,leading to the stronger binding interaction.We believe that this new fluorescent ionic liquid exhibited unique properties in detecting Al^3+in aqueous solution,which would broaden the application of ionic liquids.
基金the Ministry of Science and Innovation and State Research Agency for financial support throughout project PGC2018-097342-B-I00, including European Regional Development Fund。
文摘The main advantages of the use of ionic liquids in enhanced oil recovery are their tunability and stability in harsh environmental conditions. In this work, a comprehensive review of ionic liquids proposed to improve current chemical oil recovery methods has been presented, focusing on core flooding experiments. With an almost infinite number of possible ionic liquids, the amount of experiments carried out up to now has been very limited. However, results are promising, with additional recovery after secondary flooding of up to 32% of the original oil in place. Most formulations with ionic liquids have been proposed for sandstone reservoirs, the number of studies with carbonate cores being very scarce. The possibilities of a new room temperature surface active ionic liquid, 1-decyl-3-methylimidazolium triflate,for this application were analyzed. It was shown that it is able to drastically reduce the water/oil interfacial tension. An optimized formulation was proposed for carbonate reservoirs. After secondary flooding with brine, an additional recovery of 10.5% of original oil in place was achieved at room conditions. A combination of the proposed method followed by a polymer flooding step with polyacrylamide led to a lesser but still significant recovery, reducing the costs associated to the ionic liquid.