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1.
Summary. A review of the recent developments in the study and understanding of room temperature ionic liquids are given. An intimate picture of how and why these liquids are not crystals at ambient conditions is attempted, based on evidence from crystallographical results combined with vibrational spectroscopy and ab-initio molecular orbital calculations. A discussion is given, based mainly on some recent FT-Raman spectroscopic results on the model ionic liquid system of 1-butyl-3-methylimidazolium ([C4 mim][X]) salts. The rotational isomerism of the [C4 mim]+ cation is described: the presence of anti and gauche conformers that has been elucidated in remarkable papers by Hamaguchi et al. Such presence of a conformational equilibrium seems to be a general feature of the room temperature liquids. Then the “localized structure features” that apparently exist in ionic liquids are described. It is hoped that the structural resolving power of Raman spectroscopy will be appreciated by the reader. It is of remarkable use on crystals of known different conformations and on the corresponding liquids, especially in combination with modern quantum mechanics calculations. It is hoped that these interdisciplinary methods will be applied to many more systems in the future. A few examples will be discussed.  相似文献   

2.
A series of water soluble, surface-active ionic liquids (SAILs), namely, 1-alkyl-3-methyl imidazolium chlorides ([Cn-mim]Cl) and their mixtures with palmitic acid (PA) are investigated in Langmuir monolayers and Langmuir–Blodgett films. It is inferred from the surface pressure-area isotherms that C16-mim-IL mixes non-ideally with PA and stabilizes the binary mixed films. In addition, the residence of mim-IL at the water surface is enhanced as a function of the increasing alkyl side chain length. Generally, the compressional moduli values decrease upon increasing the content of the mim-ILs over a wide range of compositions. Furthermore, film relaxation measurements indicate that the IL component is selectively excluded from the mixed films upon achieving a certain target pressure. Brewster angle microscope images demonstrate minimal changes on the PA domains in the presence of either C4- and C8-mim-ILs, whereas presence of the hexadecyl counterpart results in the formation of condensed sheets. Atomic force microscopy imaging of deposited films show the formation of propeller-like aggregates when C8- or C16-mim-IL is present in the mixed films.  相似文献   

3.
A systematic study of densities and refractive indices of 17 room temperature ionic liquids is presented at four different temperatures ranging from 293 K to 333 K. The ionic liquids are grouped into four families: 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide, [Cnmim][Ntf2], ionic liquids (with n = 2, 4, 6, 8, 10, 12, and 14); 1-alkyl-3-methylimidazolium hexafluorophosphate, [Cnmim][PF6], ionic liquids (with n = 4, 6, 8); ionic liquids based on the trihexyl(tetradecyl)phosphonium cation, [P6 6 6 14], combined with the anions bis(trifluoromethylsulfonyl)amide, [Ntf2], acetate, [OAc], and triflate, [OTf]; and [C4mim]-based ionic liquids combined with the anions [OAc], [OTf], methylsulfate [MeSO4], and tetrafluoroborate [BF4]. The data obtained were analysed to determine the effect of (i) temperature, (ii) the alkyl chain length of the 1-alkyl-3-methylimidazolium cation, and (iii) the nature of the anion. Different empirical models for the calculation of the densities of the ionic liquids were tested. Molar refractions were also calculated from the volumetric and refractive index data and the values were discussed with the aim of checking their utility in obtaining insights on the intermolecular forces and behaviour in solution of the different ionic liquids.  相似文献   

4.
Summary. N-Toluensulfonyl-l-prolin amide was tested as catalyst in the enantioselective Michael addition of carbonyl compounds to (E)-β-nitrostyrene in nine ionic liquids under different reaction conditions. The reaction rates and enantioselectivities were strongly dependent on the ionic liquids. Change of enantioselectivity was observed too and it is attributed to both the cation and the anion of ionic liquid. The best yields (up to 98%) and enantioselectivity (70% ee) of product were obtained in a basic ionic liquid [bmim]BF4 at room temperature.  相似文献   

5.
N-Toluensulfonyl-l-prolin amide was tested as catalyst in the enantioselective Michael addition of carbonyl compounds to (E)-β-nitrostyrene in nine ionic liquids under different reaction conditions. The reaction rates and enantioselectivities were strongly dependent on the ionic liquids. Change of enantioselectivity was observed too and it is attributed to both the cation and the anion of ionic liquid. The best yields (up to 98%) and enantioselectivity (70% ee) of product were obtained in a basic ionic liquid [bmim]BF4 at room temperature.  相似文献   

6.
Two new Eu‐based ionic liquid systems, [C4mim][DTSA] : [Eu(DTSA)3] and 2[C4mim] [DTSA] : [Eu(DTSA)3] were synthesized at 120° under inert conditions from 1‐butyl‐1‐methylimidazolium ditoluenesulfonylamide ([C4mim][DTSA]). The identity and purity of the synthesized compounds were confirmed by elemental analysis, IR, Raman, and 1H‐NMR spectroscopy. As they solidify below 100° as glasses they qualify as ionic liquids. Fluorescence measurements show that the materials exhibit a strong red luminescence of high color purity. Therefore, they have the potential to be used for optical applications such as in emission displays.  相似文献   

7.
The predominant mode of strontium ion transfer from aqueous nitrate media into a series of 1-fluoroalkyl-3-methylimidazolium bis[(trifluoromethylsulfonyl)]imides containing dicyclohexano-18-crown-6 (DCH18C6) is shown to shift from cation exchange to strontium nitrato-crown ether complex partitioning as the length of the fluoroalkyl substituent is increased. Fluoroalkyl substituents are shown to be only slightly more effective than their non-fluorous analogs at inducing this shift. At the same time, the fluorinated ionic liquids (ILs) yield strontium distribution ratios as much as an order of magnitude lower than the corresponding 1-alkyl-3-methylimidazolium (Cnmim+) salts. Fluorous ILs thus appear to offer no compelling advantages over Cnmim+ ionic liquids as extraction solvents.  相似文献   

8.
A simple ionic model is revisited. The model starts with the calculation of lattice energy and thus the thermochemical radii of the ions. These radii allow the calculation of other lattice energies and through a Born–Haber cycle to obtain the enthalpy of formation. By using literature available for experimental data, the model was tested to see if it can provide reliable enthalpies of formation values. As presented in this contribution, the method only applies to binary compounds with both simple and complex ions. As examples of the usefulness of this approach, enthalpies of formation of unmeasured crystalline ionic liquids (Hmim+, C2mim+, C4mim+ and NH4+ families) and lanthanide (II) halides were determined. The latter ones were used to address the stability of lanthanide halides in states II and III.  相似文献   

9.
We investigate eight 1‐alkylpyridinium‐based ionic liquids of the form [CnPy][A] by using X‐ray photoelectron spectroscopy (XPS). The electronic environment of each element of the ionic liquids is analyzed. In particular, a reliable fitting model is developed for the C 1s region that applies to each of the ionic liquids. This model allows the accurate charge correction of binding energies and the determination of reliable and reproducible binding energies for each ionic liquid. Shake‐up/off phenomena are determinedfor both C 1s and N 1s spectra. The electronic interaction between cations and anions is investigated for both simple ionic liquids and an example of an ionic‐liquid mixture; the effect of the anion on the electronic environment of the cation is also explored. Throughout the study, a detailed comparison is made between [C8Py][A] and analogues including 1‐octyl‐1‐methylpyrrolidinium‐ ([C8C1Pyrr][A]), and 1‐octyl‐3‐methylimidazolium‐ ([C8C1Im][A]) based samples, where X is common to all ionic liquids.  相似文献   

10.
Two new diglycolamide‐based task‐specific ionic liquids (DGA? TSILs) were evaluated for the extraction of actinides and lanthanides from acidic feed solutions. These DGA? TSILs were capable of exceptionally high extraction of trivalent actinide ions, such as Am3+, and even higher extraction of the lanthanide ion, Eu3+ (about 5–10 fold). Dilution of the DGA? TSILs in an ionic liquid, C4mim+ ? NTf2?, afforded reasonably high extraction ability, faster mass transfer, and more efficient stripping of the metal ion. The nature of the extracted species was studied by slope analysis, which showed that the extracted species contained one NO3? anion, along with the participation of two DGA? TSIL molecules. Time‐resolved laser fluorescence spectroscopy (TRLFS) analysis showed a strong complexation with no inner‐sphere water molecule in the EuIII? DGA? TSIL complexes in the presence and absence of C4mim+ ? NTf2? as the diluent. The very high radiolytic stability of DGA? TSIL 6 makes it one of the most‐efficient solvent systems for the extraction of actinides under acidic feed conditions.  相似文献   

11.
We present new results on the liquid–liquid extraction of uranium (VI) from a nitric acid aqueous phase into a tri‐n‐butyl phosphate/1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (TBP/[C4mim][Tf2N]) phase. The individual solubilities of the ionic‐liquid ions in the upper part of the biphasic system are measured over the whole acidic range and as a function of the TBP concentration. New insights into the extraction mechanism are obtained through the in situ characterization of the extracted uranyl complexes by coupling UV/Vis and extended X‐ray absorption fine structure (EXAFS) spectroscopy. We propose a chemical model to explain uranium (VI) extraction that describes the data through a fit of the uranyl distribution ratio DU. In this model, at low acid concentrations uranium (VI) is extracted as the cationic complex [UO2(TBP)2]2+, by an exchange with one proton and one C4mim+. At high acid concentrations, the extraction proceeds through a cationic exchange between [UO2(NO3)(HNO3)(TBP)2]+ and one C4mim+. As a consequence of this mechanism, the variation of DU as a function of TBP concentration depends on the C4mim+ concentration in the aqueous phase. This explains why noninteger values are often derived by analysis of DU versus [TBP] plots to determine the number of TBP molecules involved in the extraction of uranyl in an ionic‐liquid phase.  相似文献   

12.
Stokes–Einstein (SE) and Stokes–Einstein–Debye (SED) relations in the neat ionic liquid (IL) [C2mim][NTf2] and IL/chloroform mixtures are studied by means of molecular dynamics (MD) simulations. For this purpose, we simulate the translational diffusion coefficients of the cations and anions, the rotational correlation times of the C(2)? H bond in the cation C2mim+, and the viscosities of the whole system. We find that the SE and SED relations are not valid for the pure ionic liquid, nor for IL/chloroform mixtures down to the miscibility gap (at 50 wt % IL). The deviations from both relations could be related to dynamical heterogeneities described by the non‐Gaussian parameter α(t). If α(t) is close to zero, at a concentration of 1 wt % IL in chloroform, both relations become valid. Then, the effective radii and volumes calculated from the SE and SED equations can be related to the structures found in the MD simulations, such as aggregates of ion pairs. Overall, similarities are observed between the dynamical properties of supercooled water and those of ionic liquids.  相似文献   

13.
At present, there is a considerable amount of work devoted to the study of the thermophysical properties of pure ionic liquids, which contrasts with the few data available for their mixtures. One of the most appealing characteristics of ionic liquids is the capability of subtly changing the chemical structure of the cation and anion in order to design appropriate solvents for specific applications. Mixtures of ionic liquids increase enormously this specificity, due to the unlimited combinations that arise from mixing two or more ionic liquids. In this context, the study of the thermophysical properties of these mixtures is revealed as a fundamental task. In this work the viscosities of the ionic liquid binary mixtures with a common ion ([C6mim] + [C2mim])[BF4], ([C6mim] + [C4mim])[BF4], [C4mim]([BF4] + [MeSO4]) and [C4mim]([PF6] + [BF4]) were determined within the temperature range (298.15–308.15) K. The temperature dependence of the viscosity for pure liquids is analyzed by means of the Vogel-Tammann-Fulcher equation and several mixing rules are applied for the mixtures.  相似文献   

14.
Liu Y  Sun X  Luo F  Chen J 《Analytica chimica acta》2007,604(2):107-113
A new material (IL923SGs) composed of ionic liquids and trialkyl phosphine oxides (Cyanex 923) for Y(III) uptake was prepared via a sol-gel method. The hydrophobic ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate (C8mim+PF6) was used as solvent medium and pore templating material. The extraction of Y(III) by IL923SGs was mainly due to the complexation of metal ions with Cyanex 923 doped in the solid silica. Ionic liquid was stably doped into the silica gel matrix providing a diffusion medium for Cyanex 923, and this will result in higher removal efficiencies and excellent stability for metal ions separation. IL923SGs were also easily regenerated and reused in the subsequent removal of Y(III) in four cycles.  相似文献   

15.
The surface active and aggregation behavior of ionic liquids of type [C n mim][X] (1-alkyl-3-methylimidazolium (mim) halides), where n = 4, 6, 8 and [X] = Cl, Br and I was investigated by using three techniques: surface tension, 1H nuclear magnetic resonance (NMR) spectroscopy, small-angle neutron scattering (SANS). A series of parameters including critical aggregation concentrations (CAC), surface active parameters and thermodynamic parameters of aggregation were calculated. The 1H NMR chemical shifts and SANS measurements reveal no evidence of aggregates for the short-chain 1-butylmim halides in water and however small oblate ellipsoidal shaped aggregates are formed by ionic liquids with 1-hexyl and 1-octyl chains. Analysis of SANS data analysis at higher concentrations of [C8mim][Cl] showed that the microstructures consist of cubically packed molecules probably through ππ and hydrogen bond interactions.  相似文献   

16.
Three new mesoporous silica materials IL15SGs (HF15SG, TF15SG and DF15SG) doped with benzo-15-crown-5 and imidazolium based ionic liquids (C8mim+PF6 ?, C8mim+BF4 ? or C8mim+NTf 2 ? ) have been prepared by a simple approach to separating lithium isotopes. The formed mesoporous structures of silica gels have been confirmed by transmission electron microscopy image and N2 gas adsorption–desorption isotherm. Imidazolium ionic liquids acted as templates to prepare mesoporous materials, additives to stabilize extractant within silica gel, and synergetic agents to separate the lithium isotopes. Factors such as lithium salt concentration, initial pH, counter anion of lithium salt, extraction time, and temperature on the lithium isotopes separation were examined. Under optimized conditions, the extraction efficiency of HF15SG, TF15SG and DF15SG were found to be 11.43, 10.59 and 13.07 %, respectively. The heavier isotope 7Li was concentrated in the solution phase while the lighter isotope 6Li was enriched in the gel phase. The solid–liquid extraction maximum single-stage isotopes separation factor of 6Li–7Li in the solid–liquid extraction was up to 1.046 ± 0.002. X-ray crystal structure analysis indicated that the lithium salt was extracted into the solid phase with crown ether forming [(Li0.5)2(B15)2(H2O)]+ complexes. IL15SGs were also easily regenerated by stripping with 20 mmol L?1 HCl and reused in the consecutive removal of lithium ion in five cycles.  相似文献   

17.
1-Alkyl-3-methylpyridinium-based ionic liquids with substituents from C2 to C10 and anions Cl? and Br? were synthesized, and their dissolving power toward the cellulose was investigated. The results of quantum-chemical calculations of molecules of ionic liquids are presented.  相似文献   

18.
蔡燕  李在均  张海朗  范旭  张锁江 《化学学报》2010,68(10):1017-1022
合成了五种新的1-烷基-2,3-二甲基咪唑二(三氟甲基磺酰)亚胺离子液体(alkyl-DMimTFSI).以离子液体作为Li/LiFeO4电池电解液,分别考察不同烷基(正丁基、正戊基、正辛基、异辛基和正癸基)对电解液理化性质、界面性质和电池行为的影响.结果表明离子液体的电化学窗口都可以达到5.6V(-0.4~5.2Vvs.Li+/Li),显示它们具有较好的电化学稳定性.加入碳酸亚乙烯酯作为添加剂后,离子液体电解液在Li负极形成稳定的固体电解质相界面膜(SEI),从而提高了Li负极的稳定性,保护了Li片不受腐蚀.电化学阻抗和循环伏安分析进一步揭示LiFeO4正极与离子液体电解液也有良好的兼容性.此外,研究还表明离子液体中烷基种类严重影响它们的电池行为.采用butyl-DMimTFSI和amyl-DMimTFSI电解液体系的电池充放电容量和可逆性明显优于另外三种离子液体,它们的首次放电容量分别达到145和152.6mAh/g,并表现出良好的充放电循环性能.因粘度最大,采用isooctyl-DMimTFSI电解液的电池首次放电容量仅为8.3mAh/g,但添加碳酸丙烯酯(质量比1∶1)稀释后首次放电容量上升至132.4mAh/g.  相似文献   

19.
A mixture of 1(3),2-di-O-acyl-3(1)-O-β-gentiobiosylglycerols was isolated from a sea isolate ofBacillus pumilus. The components of the mixture were structurally characterized by mass spectrometry and1H and13C NMR spectroscopy data for the native compounds and their derivatives. The predominant component contains two C15 acyl groups, while the second component contains C15 and C17 fatty acids. Six minor components differ in residues of fatty acids and/or their combinations. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 166–170, January, 2000.  相似文献   

20.
An NMR study of 10 l-alanine- and l-valine-containing peptides was carried out in the native [C2MIM][Cl], [C4MIM][Cl], [C6MIM][Cl], [C4MIM][BF4], [C4MIM][PF6], and [C4Py][BF4] ionic liquid media. A unique high sensitivity of the ionic liquid system to the nature of peptide and ability to tune solvent–solute interactions were observed in contrast to regular organic solvents. The l-valine peptides can be selectively dissolved in [C4MIM][Cl] and [C6MIM][Cl], whereas their solubility in [C2MIM][Cl] and other ionic liquids was dramatically lower. In spite of structural similarity between the amino acids, a distinct behavior was observed for the l-alanine peptides. Solvent–solute interactions with an ionic liquid impose significant changes, and NMR spectroscopy is a useful probe for the molecular-level and nanoscale organization of the studied systems. An even/odd effect of the number of amino acids in the peptide on molecular interactions in ionic liquids was observed. Enhancement of chemical properties of peptides in ionic liquids and application of ionic liquids in the separation of peptides are the areas of practical interest in the studied systems.  相似文献   

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