The alkylation of toluene with 1,3-pentadiene to produce pentyltoluene was carded out to obtain 2,6-dimethylnaphalene, which is an important intermediate during the production of 2,6-naphthalene dicarboxylic acid. Bas...The alkylation of toluene with 1,3-pentadiene to produce pentyltoluene was carded out to obtain 2,6-dimethylnaphalene, which is an important intermediate during the production of 2,6-naphthalene dicarboxylic acid. Based on our previous work using anhydrous AlCl3 as catalyst, [bupy]BF4-AlCl3 ionic liquids were employed to catalyze the reaction of 1,3-pentadiene with toluene. The experimental results show that [bupy]BF4-AlCl3 ionic liquids are suitable for the reaction especially when the molar ratio of AlCl3 to [bupy]BF4 is 1.75 : 1, and the reaction could proceed at the temperature as low as 0℃. It could be as active as pure AlCl3, but much more environmentally friendly.展开更多
Up to now the mechanism of Priedel-Crafts reactions catalyzed by ionic liquidhave not been fully understood, while carbocation mechanism was assumed. It was found that thesource of H^+ and the route of reaction initia...Up to now the mechanism of Priedel-Crafts reactions catalyzed by ionic liquidhave not been fully understood, while carbocation mechanism was assumed. It was found that thesource of H^+ and the route of reaction initiated the alkylation of benzene with ethylene catalyzedby [bmim]Cl/FeCl_3 ionic liquid. The fact that dewatered ionic liquids have catalytic activity forthe alkylation of benzene with ethylene suggests that there exists a new catalytic route. Thedistinctly Bronsted acid properties of 2-H in [bmim]Cl were found through FT-IR and HNMR analysis of[bmim]Cl after titration with water free KOH in alcohol solution. In addition, the chemical shiftsof proton on the [bmim]Cl ring, especially 2-H, are sensitive to the change of FeCl_3 content andshifted downfield when FeCl_3 was added into [bmim]Cl to form ionic liquid. Thus 2-H was easy to bedisengaged from imidazolium ring with formation of H^+ to initiate the reaction. Theisotope-substituted method was employed to prove this mechanism, through the GC-MS analysis ofalkylation products of deuterated benzene with ethylene. The route of alkylation catalyzed by FeCl_3ionic liquid was found to follow the carbocation mechanism, the resource of H^+ was presented andproved using HNMR analysis of ionic liquid to inspect the intensity change of 2-H. It was found thatthe intensity of 2-H reduced 23% after reaction showing that the H^+ arising from alkylationreaction was supplied by 2-H on the imidazole ring.展开更多
Abstract The study on the catalysis of ionic liquids for alkylation of benzene with 1-octadecene to synthesize LAB (linear alkylbenzenes) was performed. The results showed that the most important factor that governe...Abstract The study on the catalysis of ionic liquids for alkylation of benzene with 1-octadecene to synthesize LAB (linear alkylbenzenes) was performed. The results showed that the most important factor that governed the conversion of olefin and selectivity of LAB was reaction temperature. Moreover, the effects of different ionic liquids and molar ratio of benzene to 1-octadecene on the conversion and selectivity were obviously in different degrees. The reaction temperature, molar ratio of benzene to 1-octadecene and the amount of catalyst were lower, compared with the traditional reaction technologies. The experimental results demonstrated that the ionic liquid had higher activity at 30℃, with over 98% selectivity of monoalkylbenzene and 100% conversion of the olefin at the molar ratio 0.08 of FeCl3 in ionic liquid to 1-octadecene and 10 for benzene to 1-octadecene.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
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
Photocatalytic oxidative desulfurization of gasoline in [BMIm]Cu2Cl3 ionic liquid was studied. A 500-W high-pressure mercury lamp was used as the light source for irradiation, nano-TiO2 was used as the photocatalyst a...Photocatalytic oxidative desulfurization of gasoline in [BMIm]Cu2Cl3 ionic liquid was studied. A 500-W high-pressure mercury lamp was used as the light source for irradiation, nano-TiO2 was used as the photocatalyst and air was introduced by a gas pump to supply O2 as the oxidant. Influence of the ratio of V(ionic liquid) to V(oil) and the TiO2 addition on the desulfurization rate of gasoline was investigated. An oxidative kinetics equation was founded. The results showed that the [BMIm]CUECl3 ionic liquid was an effective extractant for the desulfurization of gasoline. The appropriate TiO2 addition was 0.05 g in 50 mL of reaction mixture. The yield of desulfurized gasoline could reach 98.2% after being subjected to reaction for 2 h under the conditions of adopting a ratio of V(ionic liquid): V(oil)=1:4, an air flow of 100 mL/min and a TiO2 addition dosage of 0.05 g. The kinetics reaction for photo-oxidation of gasoline was a first-order reaction with an apparent rate constant of 1.9664 h^-1 and a half-time of 0.3525 h.展开更多
^1H and ^13C NMR chemical shifts were determined to investigate the interactions of acetone with a room temperature ionic liquid 1-hexyl-3- methylimidazolium bromide [C6mim]Br at various mole fractions. Changes in che...^1H and ^13C NMR chemical shifts were determined to investigate the interactions of acetone with a room temperature ionic liquid 1-hexyl-3- methylimidazolium bromide [C6mim]Br at various mole fractions. Changes in chemical shifts of hydrogen nuclei and of carbon nuclei with the acetone concentration indicated the formation of hydrogen bond between anion of the ionic liquid and methyl protons of acetone. The NMR results were in good agreement with the ab initio computational results.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
The low-viscosity FeCl_(3)-based ionic liquids(ILs)prepared from the interaction of anhydrous FeCl_(3) and alkyl imidazolium bromide([1-alkyl-3-methyl-imidazolium]Br,alkyl=ethyl,butyl,hexyl,octyl)are highly effective ...The low-viscosity FeCl_(3)-based ionic liquids(ILs)prepared from the interaction of anhydrous FeCl_(3) and alkyl imidazolium bromide([1-alkyl-3-methyl-imidazolium]Br,alkyl=ethyl,butyl,hexyl,octyl)are highly effective for the denitrogenation of model oil containing quinoline or indole.The results indicate that the chain length of the alkyl group on the imidazolium cation has little influence on the N-extraction efficiency.With the selected IL[Bmim]Br/FeCl_(3),up to 99.1%of N-extraction efficiency from model oil containing quinoline can be attained at an extraction temperature of 30°C with an IL/oil mass ratio of 1/7 and an extraction time of 30 min.The indole extraction efficiency reaches 98.9%at an IL/oil mass ratio of 1:1.Moreover,the quinoline extraction efficiency remains as high as 92.3%after the IL has been recycled four times.展开更多
NH3-CH3OH system was studied by ab initio calculations at the Hartree-Fock level using the 6-31Gbasis set. Equilibrium geometries of both of its ionic (type I and II) and neutral clusters are obtained. Different disso...NH3-CH3OH system was studied by ab initio calculations at the Hartree-Fock level using the 6-31Gbasis set. Equilibrium geometries of both of its ionic (type I and II) and neutral clusters are obtained. Different dissociation channels are evaluated for I and II, respectively. The results suggest that when NH3-CH3OH is vertically ionized,CH3O + NH+ are the dominant products via a proton transfer reaction, and accompanying the dissociation of (NH3-CH3OH)+ver to NH3 + + CH3OH, intracluster charge transfer process takes place in the system.展开更多
All solid-state batteries(ASSBs)are the holy grails of rechargeable batteries,where extensive searches are ongoing in the pursuit of ideal solid-state electrolytes.Nevertheless,there is still a long way off to the sat...All solid-state batteries(ASSBs)are the holy grails of rechargeable batteries,where extensive searches are ongoing in the pursuit of ideal solid-state electrolytes.Nevertheless,there is still a long way off to the satisfactorily high(enough)ionic conductivity,long-term stability and especially being able to form compatible interfaces with the solid electrodes.Herein,we have explored ionic transport behavior and high mobility in the sub-nano pore networks in the framework structures.Macroscopically,the frameworked electrolyte behaves as a solid,and however in the(sub)-nano scales,the very limited number of solvent molecules in confinement makes them completely different from that in liquid electrolyte.Differentiated from a liquid-electrolyte counterpart,the interactions between the mobile ions and surrounding molecules are subject to dramatic changes,leading to a high ionic conductivity at room temperature with a low activation energy.Li+ions in the sub-nano cages of the network structure are highly mobile and diffuse rather independently,where the rate-limiting step of ions crossing cages is driven by the local concentration gradient and the electrostatic interactions between Li^(+)ions.This new class of frameworked electrolytes(FEs)with both high ionic conductivity and desirable interface with solid electrodes are demonstrated to work with Li-ion batteries,where the ASSB with LiFePO_(4)shows a highly stable electrochemical performance of over 450 cycles at 2℃ at room temperature,with an almost negligible capacity fade of 0.03‰ each cycle.In addition,the FE shows outstanding flexibility and anti-flammability,which are among the key requirements of large-scale applications.展开更多
In this article, series of novel bi-SOaH-functionalized ILs were synthesized using simple, efficient and economic procedure. Hammer method had been used to determine the acidity order of these ionic liquids, and the a...In this article, series of novel bi-SOaH-functionalized ILs were synthesized using simple, efficient and economic procedure. Hammer method had been used to determine the acidity order of these ionic liquids, and the acidifies of bi-SOaH-functionalized ILs were stronger than that of traditional single-SOaH-functionalized ILs. Their catalytic activities in the synthesis of N-(3-phenyl)-3- oxo-1-(phenylpropyl)acetamide were investigated and they were consistent with their acidities.展开更多
Using the ionic liquid(IL)1-octyl-3-methylimidazolium hexafluorophosphate as the extractant and methanol as the dispersion solvent,a dispersive liquid–liquid microextraction method was developed to extract silver n...Using the ionic liquid(IL)1-octyl-3-methylimidazolium hexafluorophosphate as the extractant and methanol as the dispersion solvent,a dispersive liquid–liquid microextraction method was developed to extract silver nanoparticles(AgN Ps)from environmental water samples.Parameters that influenced the extraction efficiency such as IL concentration,pH and extraction time were optimized.Under the optimized conditions,the highest extraction efficiency for AgN Ps was above 90% with an enrichment factor of 〉90.The extracted AgN Ps in the IL phase were identified by transmission electron microscopy and ultraviolet–visible spectroscopy,and quantified by inductively coupled plasma mass spectrometry after microwave digestion,with a detection limit of 0.01 μg/L.The spiked recovery of AgN Ps was 84.4% with a relative standard deviation(RSD)of 3.8%(n = 6)at a spiked level of 5 μg/L,and 89.7% with a RSD of 2.2%(n = 6)at a spiked level of 300 μg/L,respectively.Commonly existed environmental ions had a very limited influence on the extraction efficiency.The developed method was successfully applied to the analysis of Ag NPs in river water,lake water,and the influent and effluent of a wastewater treatment plant,with recoveries in the range of 71.0%–90.9% at spiking levels of 0.11–4.7 μg/L.展开更多
Nanostructured ot-Fe2O3 were prepared by precipitation followed by calcination method. Cetyltrimethylammonium bromide (CRAB) was used as surfactant. The nano α-Fe2O3 was then silanized with (3-chloropropyl)-triet...Nanostructured ot-Fe2O3 were prepared by precipitation followed by calcination method. Cetyltrimethylammonium bromide (CRAB) was used as surfactant. The nano α-Fe2O3 was then silanized with (3-chloropropyl)-triethoxysilane (CPTES) by room temperature mixing ofα-Fe2O3 and CPTES to produce silane coated ct-Fe2O3 (CIPr-Si@Fe2O3). As-synthesized CIPr-Si@Fe2O3 was functionalized via covalent grafting of benzimidazole to produce 3-(1-benzimidazole)Pr-Si@Fe2O3. This was further reacted with bromine to afford α-Fe2O3 immobilized benzimidazolium tribromide (α-Fe2O3-BIM tribromide). This ionic liquid (IL) α-Fe2O3 BIM tribromide was characterized by FT-IR, XRD, TEM, SEM, TGA, VSM, EDX and BET analysis. The as-synthesized IL tribromide was used as catalyst for one-pot synthesis of highly substituted piperidines. The method is greener in terms of solvent selection, recovery of the catalyst and efficiency.展开更多
The vitamin C(VC) in crops was successfully determined using ascorbate oxidase(AO) electrochemical biosensor based on the biocompatible poly(3,4-ethylenedioxythiophene)(PEDOT) matrices,which was easily prepare...The vitamin C(VC) in crops was successfully determined using ascorbate oxidase(AO) electrochemical biosensor based on the biocompatible poly(3,4-ethylenedioxythiophene)(PEDOT) matrices,which was easily prepared by one-step electrodeposition technique in ionic liquid microemulsions.The fabricated biosensor displayed excellent bioelectrocatalytic performance to the oxidation of VC,wide linear range,low detection limit,fast response time,good operational and storage stability,the good results of the determination of VC in vegetable crops indicated that the fabricated biosensor will be a good candidate for the physiological and biochemical studies of crops in near future.展开更多
As a binary system of BaO-Lu_2O_3-SiO_2 ternary system, Lu_2O_3-SiO_2 system was optimized and calculated by CALPHAD approach based on available phase diagram and relevant thermodynamic data of RE_2O_3-SiO_2(RE=Lu,Y...As a binary system of BaO-Lu_2O_3-SiO_2 ternary system, Lu_2O_3-SiO_2 system was optimized and calculated by CALPHAD approach based on available phase diagram and relevant thermodynamic data of RE_2O_3-SiO_2(RE=Lu,Yb,Y) binary systems as well as our experimental data of Lu_2O_3-SiO_2 system obtained by quenching experiment. The Gibbs free energy of high temperature solution was described by an ionic two-sublattice model as(Lu^(3+))P(O^(2-), SiO_2~0)Q. The calculated phase diagram below 1873 K was in good agreement with experimental data at 1573, 1773 and 1873 K. The calculated Gibbs energies of two intermediate phases Lu_2SiO_5 and Lu_2Si_2O_7, the activity of Lu_2O_3 and SiO_2 and specific heat capacities of intermediate phases agreed well with experimental results of Y_2O_3-SiO_2 system. This tentative study will offer help for the research of single-phase phosphor and related metallurgical slags, refractories, high-temperature superconductivity material systems.展开更多
BaBa1.03Ce0.8Tm0.2O3-aceramic with orthorhombic perovskite structure was prepared by conventional solid-state reaction. The conductivity and ionic transport number of BaBa1.03Ce0.8Tm0.2O3-a a were measured by ac imped...BaBa1.03Ce0.8Tm0.2O3-aceramic with orthorhombic perovskite structure was prepared by conventional solid-state reaction. The conductivity and ionic transport number of BaBa1.03Ce0.8Tm0.2O3-a a were measured by ac impedance spectroscopy and gas concentration cell methods in the temperature range of 500-900 ℃ in wet hydrogen and wet air. Using the ceramic as solid electrolyte and porous platinum as electrodes, the hydrogen-air fuel cell was constructed, and the cell performance was examined at 500-900℃. The results indicate that the specimen is a pure ionic conductor with the ionic transport number of 1 at 500-900 ℃ in wet hydrogen. In wet air, the specimen is a mixed conductor of proton, oxide ion and electron hole. The protonic transport numbers are 0.071-0.018, and the oxide ionic transport numbers are 0.273-0.365. The conductivities of Bal.03Ceo.sTmo.203 a under wet hydrogen, wet air or fuel cell atmosphere are higher than those of BaBa1.03Ce0.8Tm0.2O3-a a (RE=Y, Eu, Ho) reported previously by us. The fuel cell can work stably. At 900℃ the maximum power output density is 122.7 mWocm 2, which is higher than that of our previous cell using BaBa1.03Ce0.8Tm0.2O3-a(RE=Y, Eu, Ho) as electrolyte.展开更多
Several metal-based ionic liquids(ILs) were synthesized and used as extractants for the desulfurization of dibenzothiophene(DBT) in simulated fuel oil.The effects of several anion and metal ions,n(ILs)/n(metal...Several metal-based ionic liquids(ILs) were synthesized and used as extractants for the desulfurization of dibenzothiophene(DBT) in simulated fuel oil.The effects of several anion and metal ions,n(ILs)/n(metal) as mole ratio,V(IL)/V(oil) and extractive times on the removal ratio of DBT were investigated in detail.The results showed that[BMIM]HSO4/FeCl3(BMIM was short for l-butyl-3-methyl imidazole)was superior to the other ILs for the extractive desulfurization.A total of 100%of DBT was removed at room temperature in 5 min with V[BMIM]HSO4/Fecl3/Voil = 1:1.The extractive activity of[BMIM]HSO4/FeCl3 IL did not change almost after five runs.Extractive desulfurization of different sulfur compounds and commercial diesel fuel oil were also examined.The removal ratios of the sulfur compounds as the reaction substrates were all over 90%and the sulfur content of commercial diesel oil decreased to120 ppm from 12,400 ppm.展开更多
文摘The alkylation of toluene with 1,3-pentadiene to produce pentyltoluene was carded out to obtain 2,6-dimethylnaphalene, which is an important intermediate during the production of 2,6-naphthalene dicarboxylic acid. Based on our previous work using anhydrous AlCl3 as catalyst, [bupy]BF4-AlCl3 ionic liquids were employed to catalyze the reaction of 1,3-pentadiene with toluene. The experimental results show that [bupy]BF4-AlCl3 ionic liquids are suitable for the reaction especially when the molar ratio of AlCl3 to [bupy]BF4 is 1.75 : 1, and the reaction could proceed at the temperature as low as 0℃. It could be as active as pure AlCl3, but much more environmentally friendly.
文摘Up to now the mechanism of Priedel-Crafts reactions catalyzed by ionic liquidhave not been fully understood, while carbocation mechanism was assumed. It was found that thesource of H^+ and the route of reaction initiated the alkylation of benzene with ethylene catalyzedby [bmim]Cl/FeCl_3 ionic liquid. The fact that dewatered ionic liquids have catalytic activity forthe alkylation of benzene with ethylene suggests that there exists a new catalytic route. Thedistinctly Bronsted acid properties of 2-H in [bmim]Cl were found through FT-IR and HNMR analysis of[bmim]Cl after titration with water free KOH in alcohol solution. In addition, the chemical shiftsof proton on the [bmim]Cl ring, especially 2-H, are sensitive to the change of FeCl_3 content andshifted downfield when FeCl_3 was added into [bmim]Cl to form ionic liquid. Thus 2-H was easy to bedisengaged from imidazolium ring with formation of H^+ to initiate the reaction. Theisotope-substituted method was employed to prove this mechanism, through the GC-MS analysis ofalkylation products of deuterated benzene with ethylene. The route of alkylation catalyzed by FeCl_3ionic liquid was found to follow the carbocation mechanism, the resource of H^+ was presented andproved using HNMR analysis of ionic liquid to inspect the intensity change of 2-H. It was found thatthe intensity of 2-H reduced 23% after reaction showing that the H^+ arising from alkylationreaction was supplied by 2-H on the imidazole ring.
基金Supported by the National Natural Science Foundation of China (No.20276038) and Beijing Natural Science Foundation (No.2052010).
文摘Abstract The study on the catalysis of ionic liquids for alkylation of benzene with 1-octadecene to synthesize LAB (linear alkylbenzenes) was performed. The results showed that the most important factor that governed the conversion of olefin and selectivity of LAB was reaction temperature. Moreover, the effects of different ionic liquids and molar ratio of benzene to 1-octadecene on the conversion and selectivity were obviously in different degrees. The reaction temperature, molar ratio of benzene to 1-octadecene and the amount of catalyst were lower, compared with the traditional reaction technologies. The experimental results demonstrated that the ionic liquid had higher activity at 30℃, with over 98% selectivity of monoalkylbenzene and 100% conversion of the olefin at the molar ratio 0.08 of FeCl3 in ionic liquid to 1-octadecene and 10 for benzene to 1-octadecene.
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the Research Foundation of Hebei Province Education Department(2007440)
文摘Photocatalytic oxidative desulfurization of gasoline in [BMIm]Cu2Cl3 ionic liquid was studied. A 500-W high-pressure mercury lamp was used as the light source for irradiation, nano-TiO2 was used as the photocatalyst and air was introduced by a gas pump to supply O2 as the oxidant. Influence of the ratio of V(ionic liquid) to V(oil) and the TiO2 addition on the desulfurization rate of gasoline was investigated. An oxidative kinetics equation was founded. The results showed that the [BMIm]CUECl3 ionic liquid was an effective extractant for the desulfurization of gasoline. The appropriate TiO2 addition was 0.05 g in 50 mL of reaction mixture. The yield of desulfurized gasoline could reach 98.2% after being subjected to reaction for 2 h under the conditions of adopting a ratio of V(ionic liquid): V(oil)=1:4, an air flow of 100 mL/min and a TiO2 addition dosage of 0.05 g. The kinetics reaction for photo-oxidation of gasoline was a first-order reaction with an apparent rate constant of 1.9664 h^-1 and a half-time of 0.3525 h.
基金Ⅴ. ACKN0WLEDGMENTS This work was supported Science Foundation of China by the National Natural (No.20273019).
文摘^1H and ^13C NMR chemical shifts were determined to investigate the interactions of acetone with a room temperature ionic liquid 1-hexyl-3- methylimidazolium bromide [C6mim]Br at various mole fractions. Changes in chemical shifts of hydrogen nuclei and of carbon nuclei with the acetone concentration indicated the formation of hydrogen bond between anion of the ionic liquid and methyl protons of acetone. The NMR results were in good agreement with the ab initio computational results.
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The authors are grateful for financial support from the Doctoral Research Funds of Liaoning Petrochemical University(2019×JJ-006).
文摘The low-viscosity FeCl_(3)-based ionic liquids(ILs)prepared from the interaction of anhydrous FeCl_(3) and alkyl imidazolium bromide([1-alkyl-3-methyl-imidazolium]Br,alkyl=ethyl,butyl,hexyl,octyl)are highly effective for the denitrogenation of model oil containing quinoline or indole.The results indicate that the chain length of the alkyl group on the imidazolium cation has little influence on the N-extraction efficiency.With the selected IL[Bmim]Br/FeCl_(3),up to 99.1%of N-extraction efficiency from model oil containing quinoline can be attained at an extraction temperature of 30°C with an IL/oil mass ratio of 1/7 and an extraction time of 30 min.The indole extraction efficiency reaches 98.9%at an IL/oil mass ratio of 1:1.Moreover,the quinoline extraction efficiency remains as high as 92.3%after the IL has been recycled four times.
文摘NH3-CH3OH system was studied by ab initio calculations at the Hartree-Fock level using the 6-31Gbasis set. Equilibrium geometries of both of its ionic (type I and II) and neutral clusters are obtained. Different dissociation channels are evaluated for I and II, respectively. The results suggest that when NH3-CH3OH is vertically ionized,CH3O + NH+ are the dominant products via a proton transfer reaction, and accompanying the dissociation of (NH3-CH3OH)+ver to NH3 + + CH3OH, intracluster charge transfer process takes place in the system.
基金Singapore Ministry of Education,Grant/Award Number:A-8000186-01-00National Research Foundation(NRF)Singapore,Grant/Award Numbers:CRP NRF-CRP26-2021-0003,NRFCRP24-2020-0002A*STAR SERC CRF Award。
文摘All solid-state batteries(ASSBs)are the holy grails of rechargeable batteries,where extensive searches are ongoing in the pursuit of ideal solid-state electrolytes.Nevertheless,there is still a long way off to the satisfactorily high(enough)ionic conductivity,long-term stability and especially being able to form compatible interfaces with the solid electrodes.Herein,we have explored ionic transport behavior and high mobility in the sub-nano pore networks in the framework structures.Macroscopically,the frameworked electrolyte behaves as a solid,and however in the(sub)-nano scales,the very limited number of solvent molecules in confinement makes them completely different from that in liquid electrolyte.Differentiated from a liquid-electrolyte counterpart,the interactions between the mobile ions and surrounding molecules are subject to dramatic changes,leading to a high ionic conductivity at room temperature with a low activation energy.Li+ions in the sub-nano cages of the network structure are highly mobile and diffuse rather independently,where the rate-limiting step of ions crossing cages is driven by the local concentration gradient and the electrostatic interactions between Li^(+)ions.This new class of frameworked electrolytes(FEs)with both high ionic conductivity and desirable interface with solid electrodes are demonstrated to work with Li-ion batteries,where the ASSB with LiFePO_(4)shows a highly stable electrochemical performance of over 450 cycles at 2℃ at room temperature,with an almost negligible capacity fade of 0.03‰ each cycle.In addition,the FE shows outstanding flexibility and anti-flammability,which are among the key requirements of large-scale applications.
基金the National Natural Science Foundation ofChina(Nos.21003049,21073064)the Fundamental Research Funds for the Central Universities for financial support
文摘In this article, series of novel bi-SOaH-functionalized ILs were synthesized using simple, efficient and economic procedure. Hammer method had been used to determine the acidity order of these ionic liquids, and the acidifies of bi-SOaH-functionalized ILs were stronger than that of traditional single-SOaH-functionalized ILs. Their catalytic activities in the synthesis of N-(3-phenyl)-3- oxo-1-(phenylpropyl)acetamide were investigated and they were consistent with their acidities.
基金supported by the National Natural Science Foundation of China(No.21207124)Research Project of Beijing Municipal Education Commission(No.KM201110005009)the Special Fund for Quality Inspection Administration Public Welfare Scientific Research Funding(No.2012104001)
文摘Using the ionic liquid(IL)1-octyl-3-methylimidazolium hexafluorophosphate as the extractant and methanol as the dispersion solvent,a dispersive liquid–liquid microextraction method was developed to extract silver nanoparticles(AgN Ps)from environmental water samples.Parameters that influenced the extraction efficiency such as IL concentration,pH and extraction time were optimized.Under the optimized conditions,the highest extraction efficiency for AgN Ps was above 90% with an enrichment factor of 〉90.The extracted AgN Ps in the IL phase were identified by transmission electron microscopy and ultraviolet–visible spectroscopy,and quantified by inductively coupled plasma mass spectrometry after microwave digestion,with a detection limit of 0.01 μg/L.The spiked recovery of AgN Ps was 84.4% with a relative standard deviation(RSD)of 3.8%(n = 6)at a spiked level of 5 μg/L,and 89.7% with a RSD of 2.2%(n = 6)at a spiked level of 300 μg/L,respectively.Commonly existed environmental ions had a very limited influence on the extraction efficiency.The developed method was successfully applied to the analysis of Ag NPs in river water,lake water,and the influent and effluent of a wastewater treatment plant,with recoveries in the range of 71.0%–90.9% at spiking levels of 0.11–4.7 μg/L.
文摘Nanostructured ot-Fe2O3 were prepared by precipitation followed by calcination method. Cetyltrimethylammonium bromide (CRAB) was used as surfactant. The nano α-Fe2O3 was then silanized with (3-chloropropyl)-triethoxysilane (CPTES) by room temperature mixing ofα-Fe2O3 and CPTES to produce silane coated ct-Fe2O3 (CIPr-Si@Fe2O3). As-synthesized CIPr-Si@Fe2O3 was functionalized via covalent grafting of benzimidazole to produce 3-(1-benzimidazole)Pr-Si@Fe2O3. This was further reacted with bromine to afford α-Fe2O3 immobilized benzimidazolium tribromide (α-Fe2O3-BIM tribromide). This ionic liquid (IL) α-Fe2O3 BIM tribromide was characterized by FT-IR, XRD, TEM, SEM, TGA, VSM, EDX and BET analysis. The as-synthesized IL tribromide was used as catalyst for one-pot synthesis of highly substituted piperidines. The method is greener in terms of solvent selection, recovery of the catalyst and efficiency.
基金supported by NSFC(Nos50963002 and 51073074)Key Projects in the National Science& Technology Pillar Program in the Eleventh Five-year Plan Period of China(Nos2006BAD02A04 and 2006BAD01A01)Jiangxi Provincial Department of Education(NosGJJ11590 and GJJ10678)
文摘The vitamin C(VC) in crops was successfully determined using ascorbate oxidase(AO) electrochemical biosensor based on the biocompatible poly(3,4-ethylenedioxythiophene)(PEDOT) matrices,which was easily prepared by one-step electrodeposition technique in ionic liquid microemulsions.The fabricated biosensor displayed excellent bioelectrocatalytic performance to the oxidation of VC,wide linear range,low detection limit,fast response time,good operational and storage stability,the good results of the determination of VC in vegetable crops indicated that the fabricated biosensor will be a good candidate for the physiological and biochemical studies of crops in near future.
基金supported by the National Natural Science Foundation of China(51304086)the Science and Technology Landing Plan for Colleges of Jiangxi Province(KJLD14045)+1 种基金Foundation of Science and Technology Pillar Program in Industrial Field of Jiangxi Province(20123BBE50075)the Program of Qingjiang Excellent Young Talents,Jiangxi University of Science and Technology
文摘As a binary system of BaO-Lu_2O_3-SiO_2 ternary system, Lu_2O_3-SiO_2 system was optimized and calculated by CALPHAD approach based on available phase diagram and relevant thermodynamic data of RE_2O_3-SiO_2(RE=Lu,Yb,Y) binary systems as well as our experimental data of Lu_2O_3-SiO_2 system obtained by quenching experiment. The Gibbs free energy of high temperature solution was described by an ionic two-sublattice model as(Lu^(3+))P(O^(2-), SiO_2~0)Q. The calculated phase diagram below 1873 K was in good agreement with experimental data at 1573, 1773 and 1873 K. The calculated Gibbs energies of two intermediate phases Lu_2SiO_5 and Lu_2Si_2O_7, the activity of Lu_2O_3 and SiO_2 and specific heat capacities of intermediate phases agreed well with experimental results of Y_2O_3-SiO_2 system. This tentative study will offer help for the research of single-phase phosphor and related metallurgical slags, refractories, high-temperature superconductivity material systems.
基金Project supported by the National Natural Science Foundation of China (No. 20771079), Qing Lan Project and the Natural Science Foundation of Education Department of Jiangsu Province (No. 07KJB 150126).
文摘BaBa1.03Ce0.8Tm0.2O3-aceramic with orthorhombic perovskite structure was prepared by conventional solid-state reaction. The conductivity and ionic transport number of BaBa1.03Ce0.8Tm0.2O3-a a were measured by ac impedance spectroscopy and gas concentration cell methods in the temperature range of 500-900 ℃ in wet hydrogen and wet air. Using the ceramic as solid electrolyte and porous platinum as electrodes, the hydrogen-air fuel cell was constructed, and the cell performance was examined at 500-900℃. The results indicate that the specimen is a pure ionic conductor with the ionic transport number of 1 at 500-900 ℃ in wet hydrogen. In wet air, the specimen is a mixed conductor of proton, oxide ion and electron hole. The protonic transport numbers are 0.071-0.018, and the oxide ionic transport numbers are 0.273-0.365. The conductivities of Bal.03Ceo.sTmo.203 a under wet hydrogen, wet air or fuel cell atmosphere are higher than those of BaBa1.03Ce0.8Tm0.2O3-a a (RE=Y, Eu, Ho) reported previously by us. The fuel cell can work stably. At 900℃ the maximum power output density is 122.7 mWocm 2, which is higher than that of our previous cell using BaBa1.03Ce0.8Tm0.2O3-a(RE=Y, Eu, Ho) as electrolyte.
基金financially supported by the National Natural Science Foundation of China(No.21106032)Hebei University of Science and Technology doctor funding(No.000172)
文摘Several metal-based ionic liquids(ILs) were synthesized and used as extractants for the desulfurization of dibenzothiophene(DBT) in simulated fuel oil.The effects of several anion and metal ions,n(ILs)/n(metal) as mole ratio,V(IL)/V(oil) and extractive times on the removal ratio of DBT were investigated in detail.The results showed that[BMIM]HSO4/FeCl3(BMIM was short for l-butyl-3-methyl imidazole)was superior to the other ILs for the extractive desulfurization.A total of 100%of DBT was removed at room temperature in 5 min with V[BMIM]HSO4/Fecl3/Voil = 1:1.The extractive activity of[BMIM]HSO4/FeCl3 IL did not change almost after five runs.Extractive desulfurization of different sulfur compounds and commercial diesel fuel oil were also examined.The removal ratios of the sulfur compounds as the reaction substrates were all over 90%and the sulfur content of commercial diesel oil decreased to120 ppm from 12,400 ppm.