We synthesized one quaternary ammonium polymeric ionic liquids（PILs）P[VBTHEA]Cl and three imidazolium PILs of P[VEIm]Br, P[VEIm]BF, P[VEIm]PFby free-radical polymerization in solution. These PILs were characterized ...We synthesized one quaternary ammonium polymeric ionic liquids（PILs）P[VBTHEA]Cl and three imidazolium PILs of P[VEIm]Br, P[VEIm]BF, P[VEIm]PFby free-radical polymerization in solution. These PILs were characterized by FT-IR,H-NMR,C-NMR, TGA, XRD and SEM. Their COadsorption capacities were measured under different pressures and temperatures by constant-volume technique. It was observed that quaternary ammonium PILs of P[VBTHEA]Cl have higher adsorption capacity for COthan those imidazolium PILs, following P[VBTHEA]Cl > P[VEIm]PF> P[VEIm]BF> P[VEIm]Br, which may be ascribed to higher positive charge density on ammonium cation than that on imidazolium cation and thus stronger interaction with CO, consistent with the results from dual-mode adsorption model that ammonium PILs have much higher CObulk absorption than imidazolium PILs. COadsorption capacity of P[VBTHEA]Cl is 9.02 mg/g under 295 K and 1 bar, which is comparable to that of some other PILs, and is much higher than that of the corresponding ILs monomer. These PILs have good adsorption selectivity for COover Nand regeneration efficiency.展开更多
Molecular dynamic simulation is used to study the microstructure of four kinds of ionic liquids(ILs),[Emim]PF6,[Emim][Tf2N],[PC6,6,6,14]PF6 and [PC6,6,6,14][Tf2N] in the capture process of CO2.Radial distribution func...Molecular dynamic simulation is used to study the microstructure of four kinds of ionic liquids(ILs),[Emim]PF6,[Emim][Tf2N],[PC6,6,6,14]PF6 and [PC6,6,6,14][Tf2N] in the capture process of CO2.Radial distribution function(RDF) and spatial distribution function(SDF) are used to analyze the microscopic properties of these systems.The calculated results show that the space distribution of CO2 around ILs determines the capability of ionic liquids for capturing CO2.Based on the analysis of SDF,CO2 and PF6-are overlapped partially around [Emim]+ in [Emim]PF6-CO2 mixture.When the anion is [Tf2N]-,cations are mainly distributed on one side of [Tf2N]-near N atom,and CO2 is concentrated on two sides near the fluoroalkylgroup(?CF3),and there is little overlapped district between cation and CO2.In [PC6,6,6,14]PF6-CO2 mixture,layered structure is found and CO2 is much nearer to PF6-than [PC6,6,6,14]+.Based on the analysis of RDF,in the phosphonium-based ILs,the highest distribution densities of anions and CO2 around cations are about 6 and 3 times as their average ones respectively,while in the imidazolium-based ILs,they are about 3 and 2 respectively,this means that the distributions of CO2 and anions around the imidazolium-based ILs are more evenly distributed than those around the phosphonium-based ILs.展开更多
Hybrid adsorbents for COcapture were prepared by coassembling laponite（LP） nanosheets and 1-nbutyl-3-methylimidazolium chloride（BMIMCl）. The prepared BMIMCl/LP layered hybrids were systematically characterized. Th...Hybrid adsorbents for COcapture were prepared by coassembling laponite（LP） nanosheets and 1-nbutyl-3-methylimidazolium chloride（BMIMCl）. The prepared BMIMCl/LP layered hybrids were systematically characterized. The interlayer distance of the BMIMCl/LP layered hybrids expanded with an increasing concentration of BMIMCl, indicating that cumulative BMIMCl was intercalated into the LP layers. The efficiency of BMIMCl toward COcapture was significantly enhanced after it was immobilized within LP layers.展开更多
The strontium ions extracted from the aqueous phase into 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide(C_2mimNTf2) with dicyclohexyl-18-crown-6(DCH18C6) was stripped effectively by supercritical CO_2(s...The strontium ions extracted from the aqueous phase into 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide(C_2mimNTf2) with dicyclohexyl-18-crown-6(DCH18C6) was stripped effectively by supercritical CO_2(sc-CO_2).Hexafluoroacetylacetone(HFAA)-acetonitrile was found to be an excellent modifier of sc-CO_2 to enhance the stripping efficiency.In the orthogonal array design(OAD),OA_(25)(5~5)matrix was employed to optimize the stripping of Sr(Ⅱ) from the DCH 18C6-C_2mimNTf_2 system.Effects of five experimental factors:temperature,pressure,concentration of HFAA,static and dynamic extraction times as well as each factor at five-levels on the stripping of Sr(Ⅱ) were optimized.The effects of these parameters were treated by the analysis of variance(ANOVA).The results showed that Sr(II) could be nearly 100%extracted from the IL phase at 308 K,30 MPa,40 min of dynamic extraction and 60 mmol·L^(-1) HFAA in acetonitrile,respectively.Finally,the stripping mechanism was studied by ESI-MS.展开更多
Thermodynamic and chemical properties of liquid carbon dioxide and nitrogen（CO_（2~–）N_2） mixture under the conditions of extremely high densities and temperatures are studied by using quantum molecular dynamic（...Thermodynamic and chemical properties of liquid carbon dioxide and nitrogen（CO_（2~–）N_2） mixture under the conditions of extremely high densities and temperatures are studied by using quantum molecular dynamic（QMD） simulations based on density functional theory including dispersion corrections（DFT-D）. We present equilibrium properties of liquid mixture for 112 separate density and temperature points, by selecting densities ranging from ρ = 1.80 g/cm^3 to 3.40 g/cm^3 and temperatures from T = 500 K to 8000 K. In the range of our study, the liquid CO_（2~–）N_2 mixture undergoes a continuous transition from molecular to atomic fluid state and liquid polymerization inferred from pair correlation functions（PCFs）and the distribution of various molecular components. The insulator–metal transition is demonstrated by means of the electronic density of states（DOS）.展开更多
基金financially supported by State Key Laboratory of Organic-Inorganic Composites(oic-201601012)the International Scientific Partnership Program ISPP at King Saud University for funding this research work through ISPP#0080
文摘We synthesized one quaternary ammonium polymeric ionic liquids（PILs）P[VBTHEA]Cl and three imidazolium PILs of P[VEIm]Br, P[VEIm]BF, P[VEIm]PFby free-radical polymerization in solution. These PILs were characterized by FT-IR,H-NMR,C-NMR, TGA, XRD and SEM. Their COadsorption capacities were measured under different pressures and temperatures by constant-volume technique. It was observed that quaternary ammonium PILs of P[VBTHEA]Cl have higher adsorption capacity for COthan those imidazolium PILs, following P[VBTHEA]Cl > P[VEIm]PF> P[VEIm]BF> P[VEIm]Br, which may be ascribed to higher positive charge density on ammonium cation than that on imidazolium cation and thus stronger interaction with CO, consistent with the results from dual-mode adsorption model that ammonium PILs have much higher CObulk absorption than imidazolium PILs. COadsorption capacity of P[VBTHEA]Cl is 9.02 mg/g under 295 K and 1 bar, which is comparable to that of some other PILs, and is much higher than that of the corresponding ILs monomer. These PILs have good adsorption selectivity for COover Nand regeneration efficiency.
基金Supported by National Basic Research Program of China(No.2009CB219902)National Natural Scientific Fund of China(No.20903098No.20873152)
文摘Molecular dynamic simulation is used to study the microstructure of four kinds of ionic liquids(ILs),[Emim]PF6,[Emim][Tf2N],[PC6,6,6,14]PF6 and [PC6,6,6,14][Tf2N] in the capture process of CO2.Radial distribution function(RDF) and spatial distribution function(SDF) are used to analyze the microscopic properties of these systems.The calculated results show that the space distribution of CO2 around ILs determines the capability of ionic liquids for capturing CO2.Based on the analysis of SDF,CO2 and PF6-are overlapped partially around [Emim]+ in [Emim]PF6-CO2 mixture.When the anion is [Tf2N]-,cations are mainly distributed on one side of [Tf2N]-near N atom,and CO2 is concentrated on two sides near the fluoroalkylgroup(?CF3),and there is little overlapped district between cation and CO2.In [PC6,6,6,14]PF6-CO2 mixture,layered structure is found and CO2 is much nearer to PF6-than [PC6,6,6,14]+.Based on the analysis of RDF,in the phosphonium-based ILs,the highest distribution densities of anions and CO2 around cations are about 6 and 3 times as their average ones respectively,while in the imidazolium-based ILs,they are about 3 and 2 respectively,this means that the distributions of CO2 and anions around the imidazolium-based ILs are more evenly distributed than those around the phosphonium-based ILs.
基金sponsored by the National Science Foundation(CMMI-1562907)the financial support from the National Natural Science Foundation of China(51678511 and 51308484)+4 种基金the Open Fund of Key Laboratory of Mineralogy and Metallogeny in Chinese Academy of Sciences(KLMM20150104)the Natural Science Foundation of Hunan Province(13JJ4049)the Education Department Fund of Hunan Province(14C1094)the Major Talent Training Program of Xiangtan University(16PYZ09)the Specialized Research Fund for the Doctoral Program of Xiangtan University(12QDZ18)
文摘Hybrid adsorbents for COcapture were prepared by coassembling laponite（LP） nanosheets and 1-nbutyl-3-methylimidazolium chloride（BMIMCl）. The prepared BMIMCl/LP layered hybrids were systematically characterized. The interlayer distance of the BMIMCl/LP layered hybrids expanded with an increasing concentration of BMIMCl, indicating that cumulative BMIMCl was intercalated into the LP layers. The efficiency of BMIMCl toward COcapture was significantly enhanced after it was immobilized within LP layers.
基金Supported by the National Natural Science Foundation of China(91226112)
文摘The strontium ions extracted from the aqueous phase into 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide(C_2mimNTf2) with dicyclohexyl-18-crown-6(DCH18C6) was stripped effectively by supercritical CO_2(sc-CO_2).Hexafluoroacetylacetone(HFAA)-acetonitrile was found to be an excellent modifier of sc-CO_2 to enhance the stripping efficiency.In the orthogonal array design(OAD),OA_(25)(5~5)matrix was employed to optimize the stripping of Sr(Ⅱ) from the DCH 18C6-C_2mimNTf_2 system.Effects of five experimental factors:temperature,pressure,concentration of HFAA,static and dynamic extraction times as well as each factor at five-levels on the stripping of Sr(Ⅱ) were optimized.The effects of these parameters were treated by the analysis of variance(ANOVA).The results showed that Sr(II) could be nearly 100%extracted from the IL phase at 308 K,30 MPa,40 min of dynamic extraction and 60 mmol·L^(-1) HFAA in acetonitrile,respectively.Finally,the stripping mechanism was studied by ESI-MS.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11374217,11135012,and 11375262)the Joint Fund of the National Natural Science Foundation of Chinathe China Academy of Engineering Physics(Grant No.11176020)
文摘Thermodynamic and chemical properties of liquid carbon dioxide and nitrogen（CO_（2~–）N_2） mixture under the conditions of extremely high densities and temperatures are studied by using quantum molecular dynamic（QMD） simulations based on density functional theory including dispersion corrections（DFT-D）. We present equilibrium properties of liquid mixture for 112 separate density and temperature points, by selecting densities ranging from ρ = 1.80 g/cm^3 to 3.40 g/cm^3 and temperatures from T = 500 K to 8000 K. In the range of our study, the liquid CO_（2~–）N_2 mixture undergoes a continuous transition from molecular to atomic fluid state and liquid polymerization inferred from pair correlation functions（PCFs）and the distribution of various molecular components. The insulator–metal transition is demonstrated by means of the electronic density of states（DOS）.
