Extraction of Metal Ions from Aqueous Solutions Using Imidazolium Based Ionic Liquids

This article represents a step towards how to choose an ionic liquid as the solvent to improve metal ion (Ag⁺ and Pb²⁺) extraction. The liquid-liquid solvent extraction is proposed with the following imidazolium ionic liquids (ILs): 1-ethyl-3-ethylimidazolium, or 1-butyl-3-ethylimidazolium, or 1-hexyl-3-ethylimidazolium bis{(trifluoromethyl)sylfonyl}imide [EEIM][NTf₂], or [BEIM][NTf₂], or [HEIM][NTf₂], or 1-butyl-3-ethylimidazolium hexafluorophosphate [BEIM][PF₆], or 1-hexyl-3-ethylimidazolium hexafluorophosphate [HEIM][PF₆] and the popular 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF₆] for comparison. The effect of anion type (NTf₂⁻ versus PF₆⁻) and the effect of structural components of an ionic liquid including alkyl chain length at the cation and the ethyl substituent instead methyl at the cation, on the extraction and re-extraction processes by using dithizone as a metal chelator, were studied at 296 K. Dithizone was employed to form neutral metal-dithizone complexes with heavy metal ions to extract them from aqueous solution into the ILs. Electronic Supplementary Material  The online version of this article () contains supplementary material, which is available to authorized users. Presented at the 236th ACS National Meeting, August 17–21, Philadelphia, USA.     

Direct Correlation of Surface Tension and Surface Composition of Ionic Liquid Mixtures—A Combined Vacuum Pendant Drop and Angle-Resolved X-ray Photoelectron Spectroscopy Study

We investigated the surface tension and surface composition of various mixtures of the two ionic liquids (ILs) 1-methyl-3-octyl-imidazolium hexafluorophosphate [C₈C₁Im][PF₆] and 1,3-bis(polyethylene glycol)imidazolium iodide [(mPEG₂)₂Im]I in the temperature range from 230 to 370 K under ultraclean vacuum conditions. The surface tension was measured using a newly developed apparatus, and the surface composition was determined by angle-resolved X-ray photoelectron spectroscopy (ARXPS). In the pure ILs, the alkyl chains of [C₈C₁Im][PF₆] and the PEG chains of [(mPEG₂)₂Im]I are enriched at the IL/vacuum interface. In the mixtures, a strong selective surface enrichment of the alkyl chains occurs, which is most pronounced at low [C₈C₁Im][PF₆] contents. For the surface tension, strong deviations from an ideal mixing behaviour take place. By applying a simple approach based on the surface composition of the mixtures as deduced from ARXPS, we are able to predict and reproduce the experimentally measured temperature-dependent surface tension values with astonishingly high accuracy.     

Room temperature ionic liquid as a novel medium for liquid/liquid extraction of metal ions

Room temperature ionic liquids (RTILs) have been used as novel solvents to replace traditional volatile organic solvents in organic synthesis, solvent extraction, and electrochemistry. The hydrophobic character and water immiscibility of certain ionic liquids allow their use in solvent extraction of hydrophobic compounds. In this work, a typical room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate [C₄mim][PF₆], was used as an alternative solvent to study liquid/liquid extraction of heavy metal ions. Dithizone was employed as a metal chelator to form neutral metal-dithizone complexes with heavy metal ions to extract metal ions from aqueous solution into [C₄mim][PF₆]. This extraction is possible due to the high distribution ratios of the metal complexes between [C₄mim][PF₆] and aqueous phase. Since the distribution ratios of metal dithiozonates between [C₄mim][PF₆] and aqueous phase are strongly pH dependent, the extraction efficiencies of metal complexes can be manipulated by tailoring the pH value of the extraction system. Hence, the extraction, separation, and preconcentraction of heavy metal ions with the biphasic system of [C₄mim][PF₆] and aqueous phase can be achieved by controlling the pH value of the extraction system. Preliminary results indicate that the use of [C₄mim][PF₆] as an alternate solvent to replace traditional organic solvents in liquid/liquid extraction of heavy metal ions is very promising.     

On-Surface Metathesis of an Ionic Liquid on Ag(111)

We investigated the adsorption, surface enrichment, ion exchange, and on-surface metathesis of ultrathin mixed IL films on Ag(111). We stepwise deposited 0.5 ML of the protic IL diethylmethylammonium trifluoromethanesulfonate ([dema][TfO]) and 1.0 ML of the aprotic IL 1-methyl-3-octylimidazolium hexafluorophosphate ([C₈C₁Im][PF₆]) at around 90 K. Thereafter, the resulting layered frozen film was heated to 550 K, and the thermally induced phenomena were monitored in situ by angle-resolved X-ray photoelectron spectroscopy. Between 135 and 200 K, [TfO]⁻ anions at the Ag(111) surface are exchanged by [PF₆]⁻ anions and enriched together with [C₈C₁Im]⁺ cations at the IL/vacuum interface. Upon further heating, [dema][PF₆] and [OMIm][PF₆] desorb selectively at ∼235 and ∼380 K, respectively. Hereby, a wetting layer of pure [C₈C₁Im][TfO] is formed by on-surface metathesis at the IL/metal interface, which completely desorbs at ∼480 K. For comparison, ion enrichment at the vacuum/IL interface was also studied in macroscopic IL mixtures, where no influence of the solid support is expected.     

离子液体型表面活性剂研究

以1-甲基咪唑为原料, 制备了6个常规离子液体: 1-正丁基-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[bmim][BF₄]及[bmim][PF₆])、1-正己基-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[hmim][BF₄]及[hmim][PF₆])、1-正十六烷基-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[C₁₆mim][BF₄]及[C₁₆mim][PF₆])和4个功能化离子液体: 1-(2-羟乙基)-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[2-hemim][BF₄]及[2-hemim][PF₆])、1-乙氧羰基甲基-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[eocmmim][BF₄]及[eocmmim][PF₆]). 研究了这两类离子液体的一些物理性能, 旨在挖掘离子液体在香料香精化妆品工业中的应用价值. 分别检测了它们与一般溶剂的互溶性, 并测定了它们的表面张力和发泡性能, 实验结果表明, 仅[C₁₆mim][BF₄]和[C₁₆mim][PF₆]具有发泡性能, 发泡力分别为68和120 mm.     

Separation of no-carrier-added 109Cd from natural silver target using RTIL 1-butyl-3-methylimidazolium hexafluorophosphate

The room temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium hexafluorophosphate [C₄mim][PF₆] has various applications in the separation of a range of metal ions replacing volatile and toxic traditional organic solvents in liquid–liquid extraction systems. In this study, the RTIL [C₄mim][PF₆] was used to separate no-carrier-added (NCA) ¹⁰⁹Cd from α-particle irradiated Ag target. A natural Ag foil was bombarded by 30 MeV α-particles to produce ¹⁰⁹Cd. After the decay of all co-produced short-lived products, NCA ¹⁰⁹Cd was separated from the bulk Ag using [C₄mim][PF₆] as extractant from HNO₃ medium. Ammoniumpyrrolidine dithiocarbamate (APDC) was used as a complexing agent. At the optimum condition, 3 M HNO₃, 0.01 M APDC in presence of [C₄mim][PF₆], ~99 % bulk Ag was extracted to the IL phase, leaving NCA ¹⁰⁹Cd in the aqueous phase. The amount of Ag became negligibly small after re-extraction in the same condition. The ionic liquid was recovered by washing it with 1 M HCl.     

Synthesis and electrochemistry of 1,1′-bis(phosphino)cobaltocenium compounds

The electrochemistry of 1,1′-bis(diphenylphosphino)cobaltocenium hexafluorophosphate ([dppc][PF₆]), 1,1′-bis(dicyclohexylphosphino)cobaltocenium hexafluorophosphate ([dcpc][PF₆]), 1,1′-bis(di-iso-propylphosphino)cobaltocenium hexafluorophosphate ([dippc][PF₆]), and 1-(di-tert-butylphosphino)cobaltocenium hexafluorophosphate ([1-dtbpc][PF₆]) was examined in methylene chloride with tetrabutylammonium hexafluorophosphate as the supporting electrolyte. A reversible reductive wave followed by an irreversible wave at more negative potentials was observed. Ten new phosphinothioyl ([dppcS₂][PF₆], [dcpcS₂][PF₆], [dippcS₂][PF₆], [1-dtbpcS][PF₆], and 1,1′-bis(dicyclohexylphosphinothioyl)ferrocene) and phosphinoselenoyl derivatives ([dppcSe₂][PF₆], [dcpcSe₂][PF₆], [dippcSe₂][PF₆], [1-dtbpcSe][PF₆], and 1,1′-bis(dicyclohexylphosphinoselenoyl)ferrocene) were prepared and characterized, and the structures of eight of these compounds were determined. The electrochemistry of these phosphinochalcogenyl cobaltocenium compounds, as well as the previously prepared [dppcO₂][PF₆], displayed two reversible reductive waves at potentials less negative than that of the free phosphines. A correlation was found to exist between the Hammett substituent constant σ_p and the reduction potentials of these compounds. In addition, the phosphinoselenoyl [dppcSe₂][PF₆], [dcpcSe₂][PF₆], and [dippcSe₂][PF₆] displayed an electrochemically irreversible oxidative wave, potentially indicating an intramolecular Se-Se bonded trication. The electrochemistry of three new and five previously reported transition metal complexes of the general formula [M_nCl₂(P^∩P)][PF₆] (M = Pd or Pt, n = 1, P^∩P = dppc, dcpc or dippc; M = Au, n = 2, P^∩P = dppc or dcpc)) was also examined displaying at least two reductive waves at potentials less negative than that of the free phosphines. Comparison of the electrochemical data with that previously obtained for analogous ferrocenes indicates that a correlation exists between the reduction potentials of the cobaltocenium phosphines and the potentials at which oxidation of the ferrocene phosphines occurs. In addition, the structure of [Au₂Cl₂(dppc)][PF₆] was determined.     

Liquid structures of 1-butyl-3-methylimidazolium tetrafluoroborate and carbon dioxide mixtures by X-ray diffraction measurements

X-ray diffraction measurements for the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM][BF₄], mixed with CO₂ were carried out at high pressures using our developed polymer cell. The intermolecular distribution functions obtained for [BMIM][BF₄]–CO₂ mixtures showed that CO₂ molecules are preferentially solvated to the [BF₄]⁻ anion. The similar preferential solvation was previously observed in analogous 1-btuyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF₆], with a different anion, which is in harmony with the present results in [BMIM][BF₄]–CO₂.     

Extraction and high performance liquid chromatographic determination of 3-indole butyric acid in pea plants by using imidazolium-based ionic liquids as extractant

In this paper, imidazolium-based ionic liquids [C₄mim][PF₆], [C₆mim][PF₆], [C₈mim][PF₆], [C₆mim][BF₄] and [C₈mim][BF₄] were tested as extracting solvents for removal of 3-indole butyric acid (IBA) from aqueous media with subsequent determination using HPLC. Percent extraction of IBA was strongly affected by pH of aqueous phases and the chemical structures of ionic liquids (ILs). Extraction of IBA was quantitative in the pH values lower than pK_a of IBA. Considering both extraction and stripping efficiencies of IBA, [C₄mim][PF₆] was found to act more efficient than other studied ILs. Capacity of [C₄mim][PF₆] was 17.6 × 10⁻⁴ mmol IBA per 1.0 mL of IL. Ionic strength of aqueous phase and temperature had shown no serious effects on extraction efficiency of IBA. A preconcentration factor of 100 and a relative standard deviation of 1.16% were obtained. It was found that ionic liquid phase was reusable almost five times for extraction/stripping purposes. 3-Indole acetic acid showed interferential effect in the extraction step. In order to assess the applicability of the method, extraction and stripping of IBA from pea plants and some other samples were studied.     

Determination of triazines in honey by dispersive liquid–liquid microextraction high-performance liquid chromatography

Dispersive liquid–liquid microextraction (DLLME) high-performance liquid chromatography (HPLC) was developed for extraction and determination of triazines from honey. A room temperature ionic liquid, 1-hexyl-3-methylimidazolium hexafluorophosphate [C₆MIM][PF_6.], was used as extraction solvent and Triton X 114 was used as dispersant. A mixture of 175 μL [C₆MIM][PF₆] and 50 μL 10% Triton X 114 was rapidly injected into the 20 mL honey sample by syringe. After extraction, phase separation was performed by centrifugation and the sedimented phase was analyzed by HPLC. Some experimental parameters, such as type and volume of extraction solvent, concentration of dispersant, pH value of sample solution, salt concentration and extraction time were investigated and optimized. The detection limits for chlortoluron, prometon, propazine, linuron and prebane are 6.92, 5.84, 8.55, 8.59 and 5.31 μg kg⁻¹, respectively. The main advantages of the proposed method are simplicity of operation, low cost, high enrichment factor and extraction solvent volume at microliter level. Honey samples were analyzed by the proposed method and obtained results indicated that the proposed method provides acceptable recoveries and precisions.     

A New Simple and Efficient Synthesis of N-Aryl Phthalimides in Ionic Liquid [bmim][PF6]

Abstract

The room temperature ionic liquid [bmim][PF₆], namely 1-butyl-3-methyl-imidazolium hexafluorophosphate, is used as an alternative solvent to classic solvents for the synthesis of a series of N-aryl phthalimides in good to excellent yields.     

Synthesis of Carbonyl Compounds from Alcohols Using Electrochemically Generated Superoxide Ions in RTILs

Abstract

We show that the superoxide ion (O₂ ^??) generated electrochemically from oxygen dissolved in room-temperature ionic liquids (RTILs) reacts with primary and secondary alcohols to form the corresponding ketones and carboxylic acids, respectively. Specifically, we study the conversion of benzhydrol to benzophenone and benzyl alcohol to benzaldehyde/benzoic acid. The kinetics (e.g., rate, selectivity, and yield) for these reactions are also determined as functions of the variations in the structure of the ionic liquids. The RTILs used here are imidazolium-based cations where the functional groups on the imidazolium ring are modified. Specifically, 1-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF₆], 1-butyl-2,3-dimethylimidazolium hexafluorophosphate [bdmim][PF₆], and 1-hexyl-3-methylimidazolium hexafluorophosphate [hmim][PF₆] are used as the reaction medium. These results are compared to an ammonium-based RTIL (N-butyl-N-trimethylammonium bis(trifluoromethylsulfonyl)imide). The results show that the nucleophilic attack by the O₂ ^?? of both the RTIL and the alcohol, especially that of the H atom at the R2 position of the [bmim][PF₆] and [hmim][PF₆], greatly affects the yields. No RTIL degradation products were detected for the reactions in [bdmim][PF₆] and N-butyl-N-trimethylammonium bis(trifluoromethylsulfonyl)imide ionic liquids. For the benzyl alcohol oxidation reaction in the RTIL, N-butyl-N-trimethylammonium bis(trifluoromethylsulfonyl)imide, benzaldehyde formed did not undergo further oxidation to form benzoic acid, which may be due to the greater hydrophobicity of this RTIL. The competitive reaction kinetics between the alcohol and RTIL component must be considered in the selection of the RTIL solvent system.     

Ionic Liquid‐Carbon Nanotube Modified Screen‐Printed Electrodes and Their Potential for Adsorptive Stripping Voltammetry

Compared with paraffin oil, the use of ionic liquids as a binder in carbon paste type electrodes was shown to greatly enhance the accumulation of analytes, as illustrated with 17α‐ethynylestradiol as a model. The ionic “liquid” n‐octyl‐pyridinium hexafluorophosphate [C₈py][PF₆] was most efficient among several ionic liquids investigated. Such preconcentration allowed a [C₈py][PF₆]‐multiwalled carbon nanotubes (MWCNTs) (95 : 5 w/w) composite electrode to be useful for adsorptive stripping voltammetry. Screen‐printed electrodes modified with [C₈py][PF₆]‐MWCNTs were developed and were able to achieve high sensitivity during adsorptive stripping voltammetric measurements under optimised conditions.     

Reverse ATRP Process of Methacrylonitrile in [C4mim][PF6]

In this original experiment, an ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([C₄mim][PF₆]), was used as the reaction media for reverse atom transfer radical polymerization of methacrylonitrile (MAN) initiated by azobisisobutyronitrile (AIBN) with FeCl₃ and isophthalic acid (IA) as catalyst and ligand. The polymerization in [C₄mim][PF₆] proceeded in a well-controlled manner as evidenced by kinetic studies. Compared with the polymerization in N, N-dimethylformamide (DMF), the polymerization in [C₄mim][PF₆] not only showed better control of molecular weight and narrower molecular weight distribution but also provided more rapid reaction rate with the ratio of [MAN]:[AIBN]:[FeCl₃]:[IA] at 300:1:2:4. The block copolymer PMAN-b-PSt was obtained via a conventional ATRP process in [C₄mim][PF₆] by using the resulting PMAN as macroinitiator. [C₄mim][PF₆] and FeCl₃/IA could be easily recycled and reused and had no effect on the living nature of reverse atom transfer radical polymerization of MAN.     

Amine basicity: measurements of ion pair stability in ionic liquid media

The stability constants relevant to the formation of amine/p-nitrophenol ion pairs have been determined in [bmim][BF₄] solution, in the presence of butylamine, piperidine, and triethylamine, by using spectrophotometric measurements. In order to evaluate how the ion pair stability is affected by ionic liquid structure, piperidine has been chosen as model amine for studies in [bmim][PF₆], [bmim][NTf₂], [bm₂im][NTf₂] and in several [bmim][BF₄]/1,4-dioxane binary mixtures. Data obtained in ionic liquid solutions have been compared with those previously reported in conventional organic solvents.     

Determination of Triazines by Ultrasonic-Assisted Ionic Liquid Microextraction Coupled with High Performance Liquid Chromatography

The determination of triazine herbicides by ultrasonic‐assisted ionic liquid microextraction coupled with high‐performance liquid chromatography was described. 1‐Hexyl‐3‐methylimidazolium hexafluorophosphate ([C₆MIm][PF₆]) was used as the extraction solvent and some extraction parameters, including volume of [C₆MIm][PF₆], extraction temperature and time, salt concentration and pH values of sample solution, were examined and optimized. The isolation of the target compounds from the matrix was found to be efficient when triazines in 10 mL of sample solution was extracted with 100 µL of [C₆MIm][PF₆] for 40 min at 50°C. The detection limits for the triazine range from 0.36 to 1.41 µg·L^?1. The satisfactory recoveries (82.3% –120.3%) with relative standard deviations ≦10.1% were obtained for the four triazine herbicides from six kinds of practical water samples.     

Determination of cobalt in water samples by atomic absorption spectrometry after pre-concentration with a simple ionic liquid-based dispersive liquid-liquid micro-extraction methodology

A rapid dispersive liquid-liquid micro-extraction (DLLME) methodology based on the application of 1-hexylpyridinium hexafluorophosphate [C₆py][PF₆] ionic liquid (IL) as an extractant solvent was applied for the pre-concentration of trace levels of cobalt prior to determination by flame atomic absorption spectrometry (FAAS). 1-Phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) was employed as a chelator forming a Co-PMBP complex to extract cobalt ions from aqueous solution into the fine droplets of [C₆py][PF₆]. Some effective factors that influence the micro-extraction efficiency include the pH, the PMBP concentration, the amount of ionic liquid, the ionic strength, the temperature and the centrifugation time which were investigated and optimized. In the optimum experimental conditions, the limit of detection (3s) and the enrichment factor were 0.70 μg L⁻¹ and 60, respectively. The relative standard deviation (RSD) for six replicate determinations of 50 μg L⁻¹ Co was 2.36%. The calibration graph using the pre-concentration system was linear at levels 2–166 μg L⁻¹ with a correlation coefficient of 0.9982. The applicability of the proposed method was evaluated by the determination of trace amounts of cobalt in several water samples.      

The influence of an electric field on the wetting of an SiO2 film by ionic liquids

The electrowetting of a dielectric SiO₂ film 100 nm thick by drops (D = 2–3 mm) of [C₄mIm][PF₆], [C₆mIm][PF₆], and [C₆mIm][BTI] ionic liquids was studied at |U| ≤ 60 V in a ～10^?8 mbar vacuum. Electrocapillary curves of the dependence of the wetting angle on electric field potential were constructed with an accuracy of ±1 deg. In conformity with the Young-Lippman equation, the wetting angle θ° decreased by the parabolic law from 51° to 43° for [C₄mIm][PF₆], from 48° to 38° for [C₆mIm][PF₆], and from 35° to 27° for [C₆mIm][BTI] as |U| increased at 298 K. The electrocapillary curve branches were situated symmetrically in the (θ°, U) coordinates with respect to the line passing through the point U = 0; that is, zero-charge potential is zero for the electrowetting of the dielectric film by the ionic liquids. The capacitance of the double electrical layer at the ionic liquid-dielectric interface was determined. This value was found to be 4.65, 2.93, and 1.73 μF/m² for the electrowetting of the SiO₂ film at 298 K by the ionic liquids specified, respectively.     

Nanoscale organization of ionic liquids and their interaction with peptides probed by C NMR spectroscopy

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.