Structural studies of 1-butyl-3-methylimidazolium tetrafluoroborate/TX-100/ p-xylene ionic liquid microemulsions.

The ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4) forms nonaqueous microemulsions with p-xylene, with the aid of the nonionic surfactant TX-100. The phase behavior of the ternary system is investigated, and three microregions of the microemulsions-ionic liquid-in-oil (IL/O), bicontinuous, and oil-in-ionic liquid (O/IL)-are identified by conductivity measurements, according to percolation theory. On the basis of a phase diagram, a series of IL/O microemulsions are chosen and characterized by dynamic light scattering (DLS). The size of aggregates increases on increasing the amount of added polar component (bmimBF(4)), which is a similar phenomenon to that observed for typical water-in-oil (W/O) microemulsions, suggesting the formation of IL/O microemulsions. The microstructural characteristics of the microemulsions are investigated by FTIR and 1H NMR spectroscopy. The results indicate that the interaction between the electronegative oxygen atoms of the oxyethylene (OE) units in TX-100 and the electropositive imidazolium ring may be the driving force for the solubilization of bmimBF4 into the core of the TX-100 aggregates. In addition, the micropolarity of the microemulsions is investigated by using methyl orange (MO) as a UV/Vis spectroscopic probe. A relatively constant polarity of the microemulsion droplets is obtained in the IL microemulsion. Finally, a plausible structure for the IL/O microemulsion is presented.     

Microregion detection of ionic liquid microemulsions

Nonaqueous ionic liquid (IL) microemulsion consisting of IL, 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF(4)), surfactant TX-100, and toluene was prepared and the phase behavior of the ternary system was investigated. Electrical conductivity measurement was used for investigating the microregions of the nonaqueous IL microemulsions. On the basis of the percolation theory, the bmimBF(4)-in-toluene (IL/O), bicontinuous, and toluene-in-bmimBF(4) (O/IL) microregions of the microemulsions were successfully identified using insulative toluene as the titration phase. However, this method was invalid when conductive bmimBF(4) acted as the titration phase. The microregions obtained by conductivity measurements were further proved by electrochemical cyclic voltammetry experiments. The results indicated that the conductivity method was feasible for identifying microstructures of the nonaqueous IL microemulsions.     

Role of solubilized water in the reverse ionic liquid microemulsion of 1-butyl-3-methylimidazolium tetrafluoroborate/TX-100/benzene

The ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4) can form nonaqueous microemulsions with benzene by the aid of nonionic surfactant TX-100. The effect of water on ionic liquid-in-oil (IL/O) microemulsions was studied, and it was shown that the addition of small amount of water to the IL microemulsion contributed to the stability of microemulsion and thus increased the amount of solubilized bmimBF4 in the microemulsion. The conductivity measurements also showed that the attractive interactions between IL microdroplets were weakened, that is, the IL/O microemulsion becomes more stable in the present of some water. Fourier transform IR was carried out to analyze the states of the added water, and the result showed that these water molecules mainly behaved as bound water and trapped water, indicating that the water molecules are located in the palisade layers of the IL/O microemulsion. Furthermore, 1H NMR and 19F NMR spectra suggested that the added water molecules built the hydrogen binding network of imidazolium cations and H2O, BF4- anion and H2O, and at the same time the electronegative oxygen atoms of the oxyethylene units of TX-100 and water in the palisade layers, which made the palisade layers more firm and thus increased the stability of the microemulsion. The study can help in further understanding the formation mechanism of microemulsions. In addition, the characteristic solubilization behavior of the added water can provide an aqueous interface film for hydrolysis reactions and therefore may be used as an ideal medium to prepare porous or hollow nanomaterials.     

States of water located in the continuous organic phase of 1-butyl-3-methylimidazolium tetrafluoroborate/Triton X-100/triethylamine reverse microemulsions.

We demonstrate a novel ionic liquid (IL) microemulsion, consisting of 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4) and nonionic surfactant Triton X-100 prepared in triethylamine which is used either as an organic solvent or a Lewis base. The effects of small amounts of added water on the microstructure of the IL microemulsion are investigated by various techniques. UV/Vis spectroscopic analysis and FTIR spectra indicate that these water molecules are not solubilized into the IL pools of the microemulsions. 1H NMR spectra further show that the added water binds with triethylamine to form a surrounding OH- base environment. Some of OH- ions enter the palisade layers of the IL microemulsions and a continuous base interface is created. The unique solubilization behavior of water reveals that it is possible to use the triethylamine microemulsions as a template to prepare metal hydroxides as well as metal oxides in the microemulsions, which is not possible when using traditional microemulsions.     

The effect of water on the microstructure of 1-butyl-3-methylimidazolium tetrafluoroborate/TX-100/benzene ionic liquid microemulsions

The ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]) forms nonaqueous microemulsions with benzene with the aid of nonionic surfactant TX-100. The phase diagram of the ternary system was prepared, and the microstructures of the microemulsion were recognized. On the basis of the phase diagram, a series of ionic liquid-in-oil (IL/O) microemulsions were chosen and characterized by dynamic light scattering (DLS), which shows a similar swelling behavior to typical water-in-oil (W/O) microemulsions. The existence of IL pools in the IL/O microemulsion was confirmed by UV/Vis spectroscopic analysis with CoCl2 and methylene blue (MB) as the absorption probes. A constant polarity of the IL pool is observed, even if small amounts of water are added to the microemulsion, thus suggesting that the water molecules are solubilized in the polar outer shell of the microemulsion, as confirmed by FTIR spectra. 1H NMR spectroscopic analysis shows that these water molecules interact with the electronegative oxygen atoms of the oxyethylene (OE) units of TX-100 through hydrogen-bonding interactions, and the electronegative oxygen atoms of the water molecules attract the electropositive imidazolium rings of [bmim][BF4]. Hence, the water molecules are like a glue that stick the IL and OE units more tightly together and thus make the microemulsion system more stable. Considering the unique solubilization behavior of added water molecules, the IL/O microemulsion system may be used as a medium to prepare porous or hollow nanomaterials by hydrolysis reactions.     

Decrease of droplet size of the reverse microemulsion 1-butyl-3-methylimidazolium tetrafluoroborate/Triton X-100/cyclohexane by addition of water

In the present contribution, results concerning the role of small amounts of water in the 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4)-in-cyclohexane ionic liquid (IL) reverse microemulsions are reported. Dynamic light scattering (DLS) revealed that the size of microemulsion droplets decreased remarkably with increasing water content although water is often used as a polar component to swell reverse microemulsions. It was thus deduced that the number of microemulsion droplets was increased which was confirmed by conductivity measurements. The states of dissolved water were investigated by Fourier transform IR (FTIR) spectroscopic analysis showing that water molecules mainly act as bound water. 1H NMR along with two-dimensional rotating frame nuclear Overhauser effect (NOE) experiments (ROESY) further revealed that water molecules were mainly located in the periphery of the polar core of the microemulsion droplets and behave like a chock being inserted in the palisade layer of the droplet. This increased the curvature of the surfactant film at the IL/cyclohexane interface and thus led to the decrease of the microemulsion droplet size. The order of surfactant molecules arranged in the interface film was increased and thus induced a loss of entropy. Isothermal titration calorimetry (ITC) indicated that an enthalpy increase compensates for the loss of entropy during the process of microstructural transition.     

Association of methanol and water in ionic liquids elucidated by infrared spectroscopy using two-dimensional correlation and multivariate curve resolution

Water and methanol associations in ionic liquids (ILs) have been studied by means of FTIR spectroscopy. Spectra at different concentrations of water or methanol in ILs were obtained by means of on-line dilution using a flow injection analysis system. Spectral features in the OH stretching region revealed that most of the water and methanol molecules tended to be isolated from each other and to interact with the anion of the IL via H bonding. By means of two-dimensional correlation spectroscopy, the formation of methanol and water dimers was also detected. Multivariate curve resolution was used to recover pure spectra and concentration profiles of the different species. Methanol dimers form at concentrations higher than 0.8% (w/w) in the three studied ILs, 1-ethyl-3-methylimidazolium tetrafluoroborate (emimBF4), 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4), and 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6). Self-association of water molecules takes place in emimBF4 and bmimBF4 at a molar ratio similar to that of methanol molecules; however, water dimers cannot be detected in bmimPF6, the most hydrophobic IL studied. No evidence was found that bigger water clusters are formed in these ILs at the studied cosolvent concentrations.     

Tween80/BmimPF6/醇/甲苯体系的相行为

以环境友好型的Tween80为表面活性剂, 以醇(乙醇、正丁醇、正己醇、正辛醇、正癸醇和异戊醇)为助表面活性剂, 对离子液体1-丁基-3-甲基咪唑六氟磷酸盐(bmimPF6)和甲苯进行了微乳化实验, 绘制了不同条件下Tween80离子液体的微乳体系的拟三元相图, 考察了醇的种类、含量对单相微乳区的影响, 并用电导法研究了在乙醇为助表面活性剂情况下, 单相微乳区的结构转变. 结果表明, 当醇(异戊醇)固定时, 随着表面活性剂/醇的质量比增加, 单相微乳区的面积逐渐增大; 不同链长的直链醇对单相微乳区的面积影响与该醇在离子液体中的溶解情况有关, 单相微乳区的面积随着直链醇链长的增加而越小; 当乙醇作助表面活性剂时, 所得到的单相微乳区的面积最大, 且单相微乳区存在着O/IL(oil-in-ionic liquid)、双连续相和IL/O(ionic liquid-in-oil)三种微结构. 尤其对离子液体微乳体系的电导随油的含量的增加而最初增大的现象进行了解释, 这一现象是由于油主要起到减少离子液体中离子对或离子的积聚, 提高带电离子淌度的作用.     

Ionic liquid-assisted synthesis of silver nanorods by polyol reduction

<正>Silver nanorods have been successfully synthesized in large scale by the ethylene glycol(EG) reduction in the presence of ionic liquid(IL) 1-butyl-3-methylimidazolium tetrafluoroborate(bmimBF_4) and polyvinyl-pyrrolidone(PVP).The silver nanorods were characterized by scanning electron microscopy(SEM),high-resolution transmission electron microscopy(HRTEM),transmission electron microscopy(TEM),electron energy disperse spectroscopy(EDS) and UV-vis spectroscopy.The results showed that the uniform silver nanorods have an average diameter of about 100 nm and the aspect ratio from 15 to 20.IL,bmimBF_4 may play a role of capping agent together with PVP in the formation of silver nanorods.On the other band,bmimBF_4 may accelerate nucleation and improve the stability of the resulting Ag nanorods due to the low interface tension of IL.     

Ionic liquids in microemulsions: Formulation and characterization

In the last few decades ionic liquids (ILs) have been widely considered as a “green solvents” and they are used in various fields. ILs can be used in the formation of microemulsion as a dispersed medium, polar domain and recently as a surfactant. In this particular review our discussion is about the novel IL-based aqueous and non-aqueous microemulsions which are quite fascinating and interesting research field for scientists. Synthesis of double and triple chain containing surface active ionic liquid (SAILs) and formation of microemulsion as a surfactant with ILs as a polar core have been elaborated in this review. ILs with a certain surface activity having long alkyl chain substituents can self-aggregate and form ILs microemulsion with high-temperature stability and temperature insensitivity. Characterization of these ILs in oil microemulsion and different ultrafast processes which are performed inside these characterized systems are documented very well. We have highlighted the similarities and differences between the nonaqueous microemulsions and the aqueous microemulsions. Addition of water and effect of temperature are quite important in case of the ILs containing microemulsions.     

DEA与SDS/n-C5H11OH/H2O微乳液的相互作用

以循环伏安法研究了N,N-二乙基苯胺（DEA）与十二烷基硫酸钠（SDS）/正戊醇（n-C5H11OH）/H2O体系O/W和W/O结构微乳液的相互作用.结果表明,DEA在SDS/n-C5H11OH/H2O体系微乳液中有两种定位方式:其一,DEA分子在微乳液液滴膜相中定位于表面活性剂和助表面活性剂的极性基团附近;其二,DEA分子在微乳液液滴膜相中定位于表面活性剂疏水基团一侧.两种定位的分布与微乳液的结构和组成相关.     

Effect of polyethylene glycol (PEG-400) on the 1-butyl-3-methylimidazolium tetrafluoroborate-in-cyclohexane ionic liquid microemulsion

The effect of a common polymer, polyethylene glycol with molecular weight of 400 (PEG-400) on the microstructure of 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF₄)/Triton X-100/cyclohexane ionic liquid (IL) reverse microemulsion has been investigated. The addition of PEG-400 leaded to the linear increase of the microemulsion droplet size, in accordance with the observation of dispersed phase, showing that PEG-400 was only solubilized into the polar interior of the IL microemulsions. FTIR spectroscopic analysis indicated that the addition of PEG-400 decreased the electrostatic interaction between the oxygen atoms of OE units and the positive electrical charged imidazolium cation of bmimBF₄. At the same time, the oxygen atoms of PEG-400 can also interact with the imidazolium cation. These results suggested that small amounts of PEG-400 entered the palisade layers of the IL microemulsion. The conductivity of the IL reverse microemulsions was decreased owing to the dilution of conducting polar cores by the addition of insulative PEG-400, indicating that PEG-400 was only solubilized into the reverse IL microemulsion interior. The conclusion was further supported by viscosity measurement.     

Layered structure of room-temperature ionic liquids in microemulsions by multinuclear NMR spectroscopic studies

Microemulsions form in mixtures of polar, nonpolar, and amphiphilic molecules. Typical microemulsions employ water as the polar phase. However, microemulsions can form with a polar phase other than water, which hold promise to diversify the range of properties, and hence utility, of microemulsions. Here microemulsions formed by using a room‐temperature ionic liquid (RTIL) as the polar phase were created and characterized by using multinuclear NMR spectroscopy. ¹H, ¹¹B, and ¹⁹F NMR spectroscopy was applied to explore differences between microemulsions formed by using 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([bmim][BF₄]) as the polar phase with a cationic surfactant, benzylhexadecyldimethylammonium chloride (BHDC), and a nonionic surfactant, Triton X‐100 (TX‐100). NMR spectroscopy showed distinct differences in the behavior of the RTIL as the charge of the surfactant head group varies in the different microemulsion environments. Minor changes in the chemical shifts were observed for [bmim]⁺ and [BF₄]^? in the presence of TX‐100 suggesting that the surfactant and the ionic liquid are separated in the microemulsion. The large changes in spectroscopic parameters observed are consistent with microstructure formation with layering of [bmim]⁺ and [BF₄]^? and migration of Cl^? within the BHDC microemulsions. Comparisons with NMR results for related ionic compounds in organic and aqueous environments as well as literature studies assisted the development of a simple organizational model for these microstructures.     

Characteristics of microemulsion polymerized styrene with water-soluble versus oil-soluble initiators

The effect of oil-soluble versus water-soluble free-radical generators in the polymerization of styrene in oil-in-water (O/W) micromulsions were investigated by photon correlation spectroscopy. The microemulsions were formed by styrene, brine, sodium dodecyl sulfate (SDS), and pentanol. The polymerizations were carried out in two microemulsions that contained droplets differing by a factor of 2.4 in volume. Under the conditions of ? = 0.019 and NaCl/SDS > 2 the microemulsions were stable and the droplets were independent of one another. Both oil-soluble and water-soluble initiators produced polystyrene that contained fractions of two different sizes. In the case of the oil-soluble initiator the droplet size in the microemulsion seemed to be correlated to the size of the product whereas in the case of the water-soluble initiator, there seemed to be little relation.     

Research on electrochemical properties of nonaqueous ionic liquid microemulsions

The nonaqueous ionic liquid (IL) microemulsions composed of 1-butyl-3-methylimidazolium tetrafluoroborate, Triton X-100, and toluene were prepared and the electrochemical properties of the nonaqueous IL microemulsions were investigated in this paper. It is shown that characteristics of the nonaqueous IL microemulsions such as electrical conductivity, electrochemical window, and solubility are good, which indicate that the nonaqueous IL microemulsions can be used as electrolyte for electrochemical research. The electrochemical properties of the nonaqueous IL microemulsions were researched by cyclic voltammetry (CV) and electrochemical impedance spectroscopy methods using potassium ferricyanide as electroactive probe. It was found that the reversibility was better and the peak current densities of CV were higher for the [Fe(CN)₆]³⁻/[Fe(CN)₆]⁴⁻ electrode reaction in the nonaqueous IL microemulsions than those in IL. However, the electrochemical behavior of the probe in the nonaqueous IL microemulsions with different microenvironments (oil-in-IL, IL-in-oil, and bicontinuous) was different. The electrochemical property of the probe in the oil-in-IL microemulsion was the best, which was studied in detail.     

Comparison of electrodeposition of silver in ionic liquid microemulsions

Both ionic liquid (IL) and water are typical green solvents and have high electric conductivity. The use of IL microemulsions as templates and media for electrochemical synthesis of nano-materials is attractive. In this work, water-in-ionic liquid (W/IL) microemulsion and ionic liquid-in-water (IL/W) microemulsion were prepared, in which hydrophobic ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate was used. The cyclic voltammetry (CV) behavior and electroplating in the W/IL and IL/W microemulsion systems containing silver nitrate were investigated for the first time. Both the CV curves exhibit the presence of reduction and oxidation peaks corresponding to the deposition and dissolution of silver from the two microemulsion systems. However, the CV obtained from IL/W microemulsion system exhibits a crossover, which is different from that obtained from W/IL microemulsion system. The electrodeposits obtained from W/IL microemulsion system are nano-granular, while those obtained from IL/W microemulsion system are planar. These results are attributed to the different microenvironments of the microemulsions.     

Silver nanoparticle formation in microemulsions acting both as template and reducing agent

A novel method of making silver nanoparticles in water-in-oil microemulsions using the surfactants as both the reducing agent and as the structure-directing agent is presented. Since no external strong reducing agent is used the kinetics of the formation is slow, which makes it possible to study the silver nanoparticle formation in situ. The microemulsions used were based on either the nonionic surfactant Brij30 (C12E4), which reduces the silver ion to metallic silver and is thereby partly oxidized, or mixtures of Brij30 and AOT (sodium bis(2-ethylhexyl) sulfosuccinate, where the latter does not reduce the silver ions. The influences of silver ion and nonionic surfactant concentrations on the formation kinetics of the nanoparticles were followed in situ using UV-vis spectroscopy, and both parameters were found to have a big influence. The microemulsion droplet's size, size distribution, and shape were examined by small-angle X-ray scattering (SAXS), and the formed silver nanoparticles were studied using both transmission electron microscopy and SAXS. The SAXS measurements showed that the presence of silver nitrate does not affect the microemulsion systems noticeably and that the droplet's size and shape are retained during the particle formation. It is shown that the size and morphology of the particles do not directly follow the shape and size of the microemulsion droplets even though there is a relation between the droplet size and the radii of the formed particles.     

FTIR study of Tween80/1-butyl-3-methylimidazolium hexafluorophosphate/toluene microemulsions

With the aid of Tween80, an environmentally benign nonionic surfactant applied to medicine and food industry, the ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF₆) formed IL microemulsions with toluene. The phase diagram of the ternary system was prepared at 25 °C. It was demonstrated that there were a single-phase region and a multiple phase region in the ternary phase diagram. The single-phase region could be further divided into toluene-in-bmimPF₆, bicontinuous, and bmimPF₆-in-toluene microemulsion regions by electrical conductivity. In particular, the microstructural characteristics of the microemulsions were investigated by Fourier transform infrared spectroscopy. The results indicated that it was the hydrogen-bonded interactions between bmimPF₆ and Tween80 that might be the driving force for the solubilization of bmimPF₆ into the core of the Tween80 aggregates.     

Microenvironment Effect on the Location Distribution of Phenothiazine in Cetyltrimethylammonium Bromide/<Emphasis Type="Italic">n</Emphasis>-Pentanol/H<Subscript>2</Subscript>O W/O and Bi-continuous Microemulsions

In cetyltrimethylammonium/n-pentanol/H₂O W/O (W/O = water in oil microemulsion) mixtures and bi-continuous microemulsions, phenothiazine (PTZ) molecules exist in the membrane phase of the dispersion either with the N atom or with the S atom pointed toward the polar head of cetyltrimethylammonium (CTAB). Cyclic voltammetry has been used to investigate the effects of the compositions and structures of the microemulsions, pH, and the salt on the location distribution of PTZ in the membrane phase of the dispersion in CTAB/n-C₅H₁₁OH/H₂O W/O and bi-continuous microemulsions. The results show that the location distribution of PTZ in the membrane phase of the dispersion in microemulsions is mainly dependent on the hydrogen bond between PTZ and n-C₅H₁₁OH (or the counterion), and on the electrostatic attractive interaction between the N atom in PTZ and the polar head of CTAB.     

THE EFFECT OF ALCOHOLS WITH DIFFERENT STRUCTURES ON THE FORMATION OF WARM O/W MICROEMULSIONS

The influence of twenty five different alcohols on the formation of warm oil-in-water (O/W) microemulsions was investigated. Selected concentrations of each alcohol were added to fixed amounts of stearic acid, Tween 20 and water at 65 ° C. Fifteen alcohols formed microemulsions, at least at one of the concentrations. A pattern recognition study was performed to elucidate the activities of the alcohols by Principal Component Analysis (PCA). Linear Discriminant Analysis (LDA) was used to classify them. Two classification functions, obtained for alcohols forming / not forming microemulsions, suggest that the formation of warm O/W microemulsion is linked to the nature and the dimension/lipophilicity of the alcohol.