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1.
An important step in developing ionic-liquid-based electrolytes for lithium rechargeable batteries is obtaining a molecular-level understanding of the ionic interactions that occur in these systems. In this study, 1-ethyl-3-methylimidazolium trifluoromethansulfonate ([C2mim]CF3SO3) is complexed with LiCF3SO3, and the local structures of the CF3SO3- and [C2mim]+ ions are investigated with infrared and Raman spectroscopy. The isolation and subsequent refinement of a Li[C2mim](CF3SO3)2 crystal provides further insight into the structure of the [C2mim]CF3SO3-LiCF3SO3 solutions. Minor changes are observed in the infrared and Raman spectra of dilute [C2mim]CF3SO3-LiCF3SO3 solutions compared to pure [C2mim]CF3SO3. However, a suspension of very small Li[C2mim](CF3SO3)2 crystallites forms at a solution composition of [C2mim]CF3SO3:LiCF3SO3 = 10:1 (mole ratio), placing an upper limit on the solubility of LiCF3SO3. Essentially no changes are observed in the vibrational modes of the [C2mim]+ cations over the entire range of LiCF3SO3 compositions studied, suggesting that the addition of these compounds does not significantly perturb the local structure of the [C2mim]+ cations. The salt used in this study has a common anion with the ionic liquid; thus, the ion cloud surrounding the [C2mim]+ ions, which must be primarily composed of CF3SO3- anions, is not significantly altered with the addition of LiCF3SO3.  相似文献   

2.
The solvent and rotational relaxation of Coumarin 153 (C-153) was investigated by picosecond time-resolved fluorescence spectroscopy in a room temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium octyl sulfate ([C4mim][C8SO4]). This is a typical RTIL, which form micellar structure above certain concentration of the RTIL (0.031 M). Dynamic light scattering (DLS) measurements show that the average hydrodynamic diameter ( Dh) of a [C4mim][C8SO4]-water micelle is 2.8 (+/-0.2) nm. Both the solvent and rotational relaxation of C-153 are retarded in this micelle compared to the solvation time of a similar type of dye in neat water. However, the solvent relaxation in this ionic liquid surfactant is different from that of a conventional ionic surfactant. The slow component of the solvation dynamics in C8H17SO4Na or TX-100 micelle is on the nanoseconds time scale, whereas in [C4mim][C8SO4] micelle the same component is on the subnanoseconds time scale. The different molecular motions with different time scale is the main reason behind this difference in the solvation time in micelles composed of RTIL with other conventional micelles.  相似文献   

3.
The alkyl chain length of 1-alkyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide ([Rmim][(CF(3)SO(2))(2)N], R = methyl (m), ethyl (e), butyl (b), hexyl (C(6)), and octyl (C(8))) was varied to prepare a series of room-temperature ionic liquids (RTILs), and the thermal behavior, density, viscosity, self-diffusion coefficients of the cation and anion, and ionic conductivity were measured over a wide temperature range. The self-diffusion coefficient, viscosity, ionic conductivity, and molar conductivity change with temperature following the Vogel-Fulcher-Tamman equation, and the density shows a linear decrease. The pulsed-field-gradient spin-echo NMR method reveals a higher self-diffusion coefficient for the cation compared to that for the anion over a wide temperature range, even if the cationic radius is larger than that of the anion. The summation of the cationic and anionic diffusion coefficients for the RTILs follows the order [emim][(CF(3)SO(2))(2)N] > [mmim][(CF(3)SO(2))(2)N] > [bmim][(CF(3)SO(2))(2)N] > [C(6)mim][(CF(3)SO(2))(2)N] > [C(8)mim][(CF(3)SO(2))(2)N], which greatly contrasts to the viscosity data. The ratio of molar conductivity obtained from impedance measurements to that calculated by the ionic diffusivity using the Nernst-Einstein equation quantifies the active ions contributing to ionic conduction in the diffusion components, in other words, ionicity of the ionic liquids. The ratio decreases with increasing number of carbon atoms in the alkyl chain. Finally, a balance between the electrostatic and induction forces has been discussed in terms of the main contribution factor in determining the physicochemical properties.  相似文献   

4.
Combining spectroscopic techniques (TRES and EXAFS) and molecular dynamics simulations, we have investigated the state of trivalent europium dissolved in room-temperature ionic liquids (RTILs), as a function of the RTIL anion and in the presence of added chloride anions. The studied RTILs are based on the 1-butyl-3-methyl-imidazolium (Bumim+) cation and differ by their anionic counterparts: BF4-, PF6-, Tf- (triflate, CF3SO3-), and Tf2N- [(CF3SO2)2N-]. The results show the strong influence of the RTIL nature on the first solvation shell of europium and on its complexation with chloride. Depending on the RTIL, europium(III), which was introduced in solution as a triflate salt, is found to be solvated either by RTIL anions only or as neutral undissociated EuTf3 moieties completed by solvent anions. Kinetic effects, related to the viscosity of the RTIL and the nature of the europium salt, also markedly influence the coordination of added Cl- or F- anions to the metal.  相似文献   

5.
This study focuses on the solubility behaviors of CO2, CH4, and N2 gases in binary mixtures of imidazolium-based room-temperature ionic liquids (RTILs) using 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][Tf2N]) and 1-ethyl-3-methylimidazolium tetrafluoroborate ([C2mim][BF4]) at 40 degrees C and low pressures (approximately 1 atm). The mixtures tested were 0, 25, 50, 75, 90, 95, and 100 mol % [C2mim][BF4] in [C2mim][Tf2N]. Results show that regular solution theory (RST) can be used to describe the gas solubility and selectivity behaviors in RTIL mixtures using an average mixture solubility parameter or an average measured mixture molar volume. Interestingly, the solubility selectivity, defined as the ratio of gas mole fractions in the RTIL mixture, of CO2 with N2 or CH4 in pure [C2mim][BF4] can be enhanced by adding 5 mol % [C2mim][Tf2N].  相似文献   

6.
This article reports a study of the effect of anions on the optical Kerr effect (OKE) spectra of binary ionic liquid mixtures with one mixture comprising the 3-methyl-1-pentylimidazolium ([C 5mim] (+)) cation and the anions PF 6 (-) and CF 3CO 2 (-) (TFA (-)), and another mixture comprising the [C 5mim] (+) cation and the anions Br (-) and bis(trifluomethanesulfonyl)imide (NTf 2 (-)). The spectra were obtained by the use of optical heterodyne-detected Raman-induced Kerr Effect Spectroscopy at 295 K. The OKE spectra of the mixtures are compared with the calculated mole-fraction weighted sum of the normalized OKE spectra of the neat liquids. The OKE spectra are nearly additive for [C 5mim]Br/[C 5mim][NTf 2] mixtures, but nonadditive for [C 5mim][PF 6]/[C 5mim][TFA] mixtures. In the case of the equimolar [C 5mim][PF 6]/[C 5mim][TFA] mixture, the nonadditivity is such that the experimental OKE spectrum is narrower than the calculated OKE spectrum. The additivity or nonadditivity of OKE spectra for IL mixtures can be explained by assuming ionic liquids are nanostructurally organized into nonpolar regions and ionic networks. The ionic networks in mixtures will be characterized by "random co-networks" for anions that are nearly the same in size (PF 6 (-) and TFA (-)) and by "block co-networks" for anions that differ greatly in size (Br (-) and NTf 2 (-)).  相似文献   

7.
A UV/vis/near-IR spectroscopic study shows that in [BuMeIm][(CF3SO2)2N] hydrophobic room-temperature ionic liquid solutions, [BuMeIm]2[AnCl6] complexes, where BuMeIm+ is 1-n-butyl-3-methylimidazolium and An(IV) is Np(IV) or Pu(IV), have an octahedral An(IV) environment similar to that observed in solid complexes. Water has no influence on the absorption spectra of AnCl6(2-) complexes, indicating their stability to hydrolysis in ionic liquid. Adding [BuMeIm]Cl modifies the UV/vis/near-IR absorption spectra of An(IV) in the ionic liquid and causes solids to precipitate. The solid-state reflectance spectra of the precipitates reveal considerable differences from the corresponding An(IV) hexachloro complexes. A voltammetric study indicates that AnCl6(2-) complexes are electrochemically inert in [BuMeIm][(CF3SO2)2N] at the glassy carbon working electrode. By contrast, quasi-reversible electrochemical reduction An(IV)/An(III) and An(IV) oxidation are observed in ionic liquids in the presence of [BuMeIm]Cl. The oxidation wave of noncoordinated chloride ions interferes with the An(IV) oxidation waves. The spectroscopic and voltammetric data clearly indicate the formation of nonoctahedral actinide(IV) chloride complexes with a Cl-/An(IV) ratio exceeding 6/1 in [BuMeIm][(CF3SO2)2N] in excess chloride ions.  相似文献   

8.
Light scattering and dielectric spectroscopy measurements were performed on the room temperature ionic liquid (RTIL) [C4mim][NTf2] in a broad temperature and frequency range. Ionic conductivity was used to estimate self-diffusion of ions, while light scattering was used to study structural relaxation. We demonstrate that the ionic diffusion decouples from the structural relaxation process as the temperature of the sample decreases toward T(g). The strength of the decoupling appears to be significantly lower than that expected for a supercooled liquid of similar fragility. The structural relaxation process in the RTIL follows well the high-temperature mode coupling theory (MCT) scenario. Using the MCT analysis we estimated the dynamic crossover temperature in [C4mim][NTf2] to be T(c) ~ 225 ± 5 K. However, our analysis reveals no sign of the dynamic crossover in the ionic diffusion process.  相似文献   

9.
张薇  丁永萍  张宇  陈霞  宋溪明 《化学通报》2015,78(4):330-336
本文首次将一系列含有不同酸性咪唑阳离子和不同杂多酸阴离子的杂多酸离子液体[C4mim]3PW12O40、[COOH-Cmim] 3PW12O40、[SO3H-C3mim]3PW12O40、[SO3H-C3mim]3PMo12O40和[SO3H-C3mim]4 SiW12O40作为催化剂,乙腈为萃取剂,H2O2为氧化剂,用于催化含二苯并噻吩、苯并噻吩及噻吩模型油的萃取氧化脱硫研究中.实验结果显示,杂多酸离子液体催化燃油脱硫性能不仅与阳离子的酸性强弱有关,而且与阴离子结构密切相关.阳离子的催化活性顺序为:[SO3H-C3mim]+>[COOH-Cmim]+>[C4mim]+;阴离子的催化活性顺序为PW12O403-> PMo12O403-> SiW12O404-.其中[SO3H-C3 mim]3 PW12O40催化活性最高,在60℃反应40min的条件下,二苯并噻吩的转化率约为100%,催化不同硫化物的转化率为:二苯并噻吩>苯并噻吩>噻吩.此外,该杂多酸离子液体循环使用5次催化活性仅略有下降.  相似文献   

10.
Lithium salt solutions of Li(CF3SO2)2N, LiTFSI, in a room-temperature ionic liquid (RTIL), 1-butyl-2,3-dimethyl-imidazolium cation, BMMI, and the (CF3SO2)2N(-), bis(trifluoromethanesulfonyl)imide anion, [BMMI][TFSI], were prepared in different concentrations. Thermal properties, density, viscosity, ionic conductivity, and self-diffusion coefficients were determined at different temperatures for pure [BMMI][TFSI] and the lithium solutions. Raman spectroscopy measurements and computer simulations were also carried out in order to understand the microscopic origin of the observed changes in transport coefficients. Slopes of Walden plots for conductivity and fluidity, and the ratio between the actual conductivity and the Nernst-Einstein estimate for conductivity, decrease with increasing LiTFSI content. All of these studies indicated the formation of aggregates of different chemical nature, as it is corroborated by the Raman spectra. In addition, molecular dynamics (MD) simulations showed that the coordination of Li+ by oxygen atoms of TFSI anions changes with Li+ concentration producing a remarkable change of the RTIL structure with a concomitant reduction of diffusion coefficients of all species in the solutions.  相似文献   

11.
Effects of Lewis acid BF3·OEt2, and BrCnsted acids TsOH, CF3COOH, H3PO4, and HCIO4 as cocatalyst respectively on the ligand-free palladium-catalyzed amidocarbonylation were investigated. SO3H-functional ionic liquids 1-methyl-3-(4-sulfonic acid)butylimidazolium hydrosulfate [MIm(CH2)4803H][HSO4] and 1-methyl-3-(4-sulfonic acid)butylimidazolium triflate [MIm(CH2)4SO3H][OTf] were firstly employed as cocatalysts instead of these Lewis acid and Brφnsted acids. By using a ligand-free and weak corrosive catalyst in situ prepared form PdBr2, LiBr.H2O, and [MIm(CH2)4SO3H][OTf], the arnidocarbo- nylation of benzaldehyde, acetamide, and CO could proceed smoothly and afford N-acetyl-α-phenylglycine with yield of 58% in [C6mim]PF6 medium.  相似文献   

12.
Solvation dynamics in four imidazolium cation based room temperature ionic liquids (RTIL) have been calculated by using the recently measured dielectric relaxation data [ J. Phys. Chem. B 2008, 112, 4854 ] as an input in a molecular hydrodynamic theory developed earlier for studying solvation energy relaxation in polar solvents. Coumarin 153 (C153), 4-aminophthalimide (4-AP), and trans-4-dimethylamino-4'-cyanostilbene (DCS) have been used as probe molecules for this purpose. The medium response to a laser-excited probe molecule in an ionic liquid is approximated by that in an effective dipolar medium. The calculated decays of the solvent response function for these RTILs have been found to be biphasic and the decay time constants agree well with the available experimental and computer simulation results. Also, no probe dependence has been found for the average solvation times in these ionic liquids. In addition, dipolar solvation dynamics have been predicted for two other RTILs for which experimental results are not available yet. These predictions should be tested against experiments and/or simulation studies.  相似文献   

13.
A series of room-temperature ionic liquids (RTILs) were prepared with different cationic structures, 1-butyl-3-methylimidazolium ([bmim]), 1-butylpyridinium ([bpy]), N-butyl-N-methylpyrrolidinium, ([bmpro]), and N-butyl-N,N,N-trimethylammonium ([(n-C(4)H(9))(CH(3))(3)N]) combined with an anion, bis(trifluoromethane sulfonyl)imide ([(CF(3)SO(2))(2)N]), and the thermal property, density, self-diffusion coefficients of the cation and anion, viscosity, and ionic conductivity were measured over a wide temperature range. The self-diffusion coefficient, viscosity, ionic conductivity, and molar conductivity follow the Vogel-Fulcher-Tamman equation for temperature dependencies, and the best-fit parameters have been estimated, together with the linear fitting parameters for the density. The relative cationic and anionic self-diffusion coefficients for the RTILs, independently determined by the pulsed-field-gradient spin-echo NMR method, appear to be influenced by the shape of the cationic structure. A definite order of the summation of the cationic and anionic diffusion coefficients for the RTILs: [bmim][(CF(3)SO(2))(2)N] > [bpy][(CF(3)SO(2))(2)N] > [bmpro][(CF(3)SO(2))(2)N] > [(n-C(4)H(9))(CH(3))(3)N][(CF(3)SO(2))(2)N], has been observed, which coincides with the reverse order to the viscosity data. The ratio of molar conductivity obtained from the impedance measurements to that calculated by the ionic diffusivity using the Nernst-Einstein equation quantifies the active ions contributing to ionic conduction in the diffusion components and follows the order: [bmpro][(CF(3)SO(2))(2)N] > [(n-C(4)H(9))(CH(3))(3)N][(CF(3)SO(2))(2)N] > [bpy][(CF(3)SO(2))(2)N] > [bmim][(CF(3)SO(2))(2)N] at 30 degrees C.  相似文献   

14.
Stability of neat hydrophobic Room-Temperature Ionic Liquids (RTIL) [BuMeIm]X, where [BuMeIm]+ is 1-butyl-3-methylimidazolium and X- is PF6-, and (CF3SO2)2N-, was studied under gamma radiolysis (137Cs) in an argon atmosphere and in air. It was found that the density, surface tension, and refraction index of RTILs are unchanged even by an absorbed dose of approximately 600 kGy. Studied RTILs exhibit considerable darkening when subjected to gamma irradiation. The light absorbance of ionic liquids increases linearly with the irradiation dose. Water has no influence on radiolytic darkening. A comparative study of [BuMeIm]X and [Bu4N][Tf2N] leads to the conclusion that the formation of colored products is related to gamma radiolysis of the [BuMeIm]+ cation. The radiolytic darkening kinetics of RTILs is influenced by the anions as follows: Cl- < (CF3SO2)2N- < PF6-. Electrospray ionization mass spectrometry and NMR analysis reveal the presence of nonvolatile radiolysis products at concentrations below 1 mol% for an absorbed dose exceeding 1200 kGy. Initial step of BuMeIm+ cation radiolysis is the loss of the Bu* group, the H* atom from the 2 position on the imidazolium ring, and the H* atom from the butyl chain. Radiolysis of ionic liquid anions yields F* and CF3* from PF6- and [Tf2N]-, respectively. Recombinations of these primary products of radiolysis lead to various polymeric and acidic species.  相似文献   

15.
The electrochemical oxidation of dissolved hydrogen gas has been studied in a range of room-temperature ionic liquids (RTILs), namely [C(2)mim][NTf(2)], [C(4)mim][NTf(2)], [N(6,2,2,2)][NTf(2)], [P(14,6,6,6)][NTf(2)], [C(4)mpyrr][NTf(2)], [C(4)mim][BF(4)], [C(4)mim][PF(6)], [C(4)mim][OTf], and [C(6)mim]Cl on a platinum microdisk electrode of diameter 10 microm. In all cases, except [C(6)mim]Cl, a broad quasi-electrochemically reversible oxidation peak between 0.3 to 1.3 V vs Ag was seen prior to electrode activation ([C(6)mim]Cl showed an almost irreversible wave). When the electrode was pre-anodized ("activated") at 2.0 V vs Ag for 1 min, the peak separations became smaller, and the peak shape became more electrochemically reversible. It is thought that the electrogenerated protons chemically combine with the anions (A-) of the RTIL. The appearance and position of the reverse (reduction) peak on the voltammograms is thought to depend on three factors: (1) the stability of the protonated anion, HA, (2) the position of equilibrium of the protonation reaction HA<==> H+ + A- , and (3) any follow-up chemistry, e.g., dissociation or reaction of the protonated anion, HA. This is discussed for the five different anions studied. The reduction of HNTf(2) was also studied in two [NTf(2)]- -based RTILs and was compared to the oxidation waves from hydrogen. The results have implications for the defining of pKa in RTIL media, for the development of suitable reference electrodes for use in RTILs, and in the possible amperometric sensing of H2 gas.  相似文献   

16.
The specific interaction of N-tetradecylisoquinolinium (C(14)Iq+) with Cl- and Br- has been detected in the voltammetry of ion transfer and electrocapillarity at the interface between an aqueous solution (W) and a room-temperature ionic liquid (RTIL), N-tetradecylisoquinolinium bis(pentafluoroethylsulfonyl)imide ([C(14)Iq+][C(2)C(2)N-]). This specific interaction also makes the transfer of Cl- and Br- into [C(14)Iq+][C(2)C(2)N-] energetically more favorable in comparison with that of F- and SO(4)(2-). The width of the polarized potential window in ion-transfer voltammetry at the [C(14)Iq+][C(2)C(2)N-]|W interface is significantly narrower because of the transfer of anions from W to RTIL. The degree of affinity of the anion with C(14)Iq+ agrees with the Hofmeister series. Such an ion-pair formation of anions in W with cations in the RTIL is much weaker when the cation constituting the RTIL is a symmetric tetraheptylammonium ion.  相似文献   

17.
室温离子液体对氨基苯磺酸的萃取性能   总被引:8,自引:0,他引:8  
樊静  范云场  王键吉  崔凤灵 《化学学报》2006,64(14):1495-1499
系统研究了[C4mim][PF6], [C6mim][PF6], [C6mim][BF4]和[C8mim][BF4]室温离子液体对间氨基苯磺酸、对氨基苯磺酸稀水溶液的萃取平衡. 实验结果表明: 萃取温度和相体积比的变化对分配比影响不大; 水相pH值对萃取平衡有较大的影响, 氨基苯磺酸在离子液体/水体系中的分配比在pH=4.2时达到最大值; 水相中CaCl2或Na2SO4的存在能较大幅度地提高氨基苯磺酸的分配比; 离子液体的阴离子的性质对分配比有显著的影响, 阴离子为[BF4]的离子液体对氨基苯磺酸的萃取能力大于阴离子为[PF6]的离子液体; 咪唑环上烷基链的长度也对萃取效果有一定的影响. 在所研究的离子液体中, [C6mim][BF4]和[C8mim][BF4]对氨基苯磺酸有较好的萃取性能, 且萃取相中的氨基苯磺酸可回收利用, 离子液体也可循环使用.  相似文献   

18.
1-Allyl-3-butylimidazolium bromide ionic liquid [AyBIm]Br was prepared and used for the modification of mercaptopropyl-functionalized silica through surface radical chain-transfer addition. The obtained ionic liquid-modified silica (SiImBr) was characterized by elemental analysis, infrared spectroscopy, NMR spectroscopy, and thermogravimetric analysis. The selective retention behaviours of polycyclic aromatic hydrocarbons (PAHs) including some positional isomers were investigated using SiImBr as a stationary phase in reversed-phase liquid chromatography. The results showed that SiImBr presented multiple interactions including hydrophobic, π–π, and ion–dipole interactions during the separation of PAHs and dipolar compounds. However, it is proposed that π–π and ion–dipole interactions play important roles in the separation of PAHs and dipolar compounds. These results indicate that the ionic liquid-modified silica stationary phase is promising for future applications. A commercially available monomeric octadecylated silica (ODS) column and a custom-made poly(styrene)-grafted silica (Sil-Stn) column were used as references.  相似文献   

19.
We determined the vapor pressures of aqueous solutions of 1-ethyl-3-methylimidazolium ([C 2mim])-based ionic liquids (IL) with counteranions, tetrafluoroborate (BF 4 (-)), trifluoromethanesulfonate (OTF (-)), and iodide (I (-)). Because in literature the evidence is accumulating and pointing to the fact that ionic liquid ions do not dissociate in aqueous media for the most of the concentration range, we analyzed the vapor pressure data on the basis of binary mixture, and the excess chemical potentials of each component were calculated. From these, the intermolecular interactions in terms of excess chemical potential and hence the concentration fluctuations were evaluated. Though any further discussion into the mixing schemes of the mixture awaits the excess partial molar enthalpy and hence the excess partial molar entropy data, the net interaction in terms of excess chemical potential indicates that the affinity of each IL is ranked in the descending order [C 2mim]I > [C 2mim]OTF > [C 2mim]BF 4. This is consistent with our earlier findings that [C 2mim] (+) is modestly amphiphilic with almost equal hydrophobicity and hydrophilicity, I (-) is a hydrophile, and OTF (-) is amphiphilic, and BF 4 (-) is believed to be strongly hydrophobic.  相似文献   

20.
采用两步法合成了新型功能化离子液体1-甲氧基乙基-3-甲基咪唑甘氨酸([C_3O_1mim][Gly]),并研究了其对CO_2的吸收性能.利用核磁共振、红外光谱及热重分析等手段进行表征,验证了该离子液体的结构,且发现其具有较高的热稳定性.对比单乙醇胺(MEA),考察了[C_3O_1mim][Gly]在不同温度下对CO_2的捕集能力,结果表明,[C_3O_1mim][Gly]在40℃下的吸收容量可达1.26 mol CO_2/mol IL,远高于MEA,这表明[C_3O_1mim][Gly]对CO_2具有良好的吸收能力,吸收容量随着温度升高而降低.该离子液体同时具有良好的循环稳定性,进行5次吸收解吸操作后仍可保持较高的CO_2吸收量.对该离子液体吸收CO_2进行了动力学研究,结果表明,Pseudo-second-order模型能够较好地描述该吸收过程.  相似文献   

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