[Show abstract][Hide abstract] ABSTRACT: The dissolution of metal oxides in an acid-saturated ionic liquid, followed by selective stripping of the dissolved metal ions to an aqueous phase is proposed as a new ionometallurgical approach for the processing of metals in ionic liquids. The hydrophobic ionic liquid trihexyl(tetradecyl)phosphonium chloride (Cyphos IL 101) saturated with a concentrated aqueous hydrochloric acid solution was used to dissolve CaO, NiO, MnO, CoO, CuO, ZnO and Fe2O3. It was found that nickel(II) and calcium(II) could be separated from all other transition metals present in the ionic liquid phase by stripping at high chloride concentrations. By scrubbing the ionic liquid solutions phase with water, manganese(II) and cobalt(II) could be stripped together with a fraction of iron(III) and copper(II), leaving zinc(II) and the remainder of copper(II) and iron(III) in the ionic liquid phase. These metal ions could be removed from the ionic liquid using ammonia. Copper(II) and zinc(II) formed ammine complexes and were back-extracted, while iron(III) precipitated as iron(III) hydroxide. After removal of all the metals present in the ionic liquid phase, the ionic liquid was prepared for reuse. Unfortunately, the mutual separations nickel–calcium, cobalt–manganese, or zinc–copper could not be achieved. This system would be useful when nickel is the metal of interest, since separation of nickel from all other transition metals present in the solution is achieved by one stripping step.
[Show abstract][Hide abstract] ABSTRACT: Metal oxides were found to dissolve in different imidazolium ionic liquids with a hydrogen atom in the C2 position of the imidazolium ring, but not if a methyl substituent was present in the C2 position. The crystal structure of the product that crystallised from an ionic liquid containing dissolved silver(i) oxide showed that this was a silver(i) carbene complex. The presence of carbenes in solution was proven by (13)C NMR spectroscopy and the reactions were also monitored by Raman spectroscopy. The dissolution of other metal oxides, namely copper(ii) oxide, zinc(ii) oxide and nickel(ii) oxide, was also studied in imidazolium ionic liquids and it was found that stable zinc(ii) carbenes were formed in solution, but these did not crystallise under the given experimental conditions. A crystalline nickel(ii) carbene complex could be obtained from a solution of nickel(ii) chloride dissolved in a mixture of 1-butyl-3-methylimidazolium and 1-ethyl-3-methylimidazolium acetate.
[Show abstract][Hide abstract] ABSTRACT: The electrochemical dissolution of Pt in several ionic liquids (ILs) was studied. Different ILs were tested assessing their potential to dissolve Pt. Dissolution rate and current efficiency were evaluated. The main focus was on Cl containing ILs: first generation, eutectic-based ILs and second generation ILs with discrete anions. Pt dissolution only occurred in type 1 eutectic-based ILs with a max. dissolution rate of 192.2 g m−2 h−1 and a max. current efficiency of 99 % for the ZnCl2–1-ethyl-3-methylimidazolium chloride IL, and 9.090 g m−2 h−1 and 96 % for the 1:1 ZnCl2–choline chloride IL. The dissolution occurred through the formation of [PtClx]y− complexes. To form these complexes, addition of a metal chloride was necessary. Furthermore, an IL with an electrochemical window of 1.5 V, preferably 2.0 V was required to achieve Pt dissolution. The added metal salt needed to have a higher decomposition potential than 1.5 V or should be a Pt salt.
[Show abstract][Hide abstract] ABSTRACT: The electrochemical dissolution of Pt in several ionic liquids (IL’s) was studied. Different IL’s were tested assessing their potential to dissolve Pt. Dissolution rate and current efficiency were evaluated. The main focus was on Cl containing IL’s: first generation, eutectic based IL’s and second generation IL’s with discrete anions. Pt dissolution only occurred in type 1 eutectic-based IL’s with a max. dissolution rate of 192.2 g m−2 h−1 and a max. current efficiency of 99 % for the ZnCl2-1-ethyl-3-methylimidazolium chloride IL, and 9.090 g m−2 h−1 and 96 % for the 1:1 ZnCl2–choline chloride ionic liquid. The dissolution occurred via the formation of [PtClx
]y− complexes. To form these complexes, addition of a metal chloride was necessary. Furthermore, an IL with an electrochemical window of 1.5 V, preferably 2.0 V is required to achieve Pt dissolution. The added metal salt needed to have a higher decomposition potential than 1.5 V or should be a Pt salt.
[Show abstract][Hide abstract] ABSTRACT: The proof-of-principle for the separation of metals by solvent extraction using two mutually immiscible ionic liquids is given. Cobalt was extracted from the ionic liquid 1-ethyl-3-methylimidazolium chloride to the ionic liquid trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate. A distribution ratio of 44 was obtained. Cobalt could be selectively separated from nickel, with a separation factor of 207. The extraction mechanism was elucidated using UV-VIS absorption measurements. The mutual solubility between the two ionic liquids was determined by (1)H NMR. Processing steps such as washing, stripping and regeneration of the ionic liquid phases are discussed.
[Show abstract][Hide abstract] ABSTRACT: A continuous ionic liquid extraction process using the ionic liquid trihexyl(tetradecyl)phosphonium chloride (Cyphos® IL 101) has been developed for the selective extraction of cobalt from nickel. The performance of this continuous extraction process is competitive with that of currently applied industrial processes. Moreover, the elimination of volatile odorous compounds from the extraction phase leads to environmentally friendlier and healthier working conditions.
Green Chemistry 01/2013; 15(11-11):3160. DOI:10.1039/c3gc41519h · 8.02 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: A green solvent extraction process for the separation of cobalt from nickel, magnesium and calcium in chloride medium was developed, using undiluted phosphonium-based ionic liquids as extractants. Cobalt was extracted to the ionic liquid phase as the tetrachlorocobaltate(II) complex, leaving behind nickel, magnesium and calcium in the aqueous phase. Manganese is interfering in the separation process. The main advantage of this ionic liquid extraction process is that no organic diluents have to be added to the organic phase, so that the use of volatile organic compounds can be avoided. Separation factors higher than 50000 were observed for the cobalt/nickel separation from 8 M HCl solution. After extraction, cobalt can easily be stripped using water and the ionic liquid can be reused as extractant, so that a continuous extraction process is possible. Up to 35 g L−1 of cobalt can be extracted to the ionic liquid phase, while still having a distribution coefficient higher than 100. Instead of hydrochloric acid, sodium chloride can be used as a chloride source. The extraction process has been upscaled to batch processes using 250 mL of ionic liquid. Tri(hexyl)tetradecylphosphonium chloride, tri(butyl)tetradecylphosphonium chloride, tetra(octyl)phosphonium bromide, tri(hexyl)tetradecylphosphonium bromide and Aliquat 336 have been tested for their performance to extract cobalt from an aqueous chloride phase to an ionic liquid phase. Tri(hexyl)tetradecylphosphonium chloride (Cyphos IL 101) turned out to be the best option as the ionic liquid phase, compromising between commercial availability, separation characteristics and easiness to handle the ionic liquid.
Green Chemistry 06/2012; 14(6):1657-1665. DOI:10.1039/C2GC35246J · 8.02 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Uranium(VI) oxide has been dissolved in three different ionic liquids functionalized with a carboxyl group: betainium bis[(trifluoromethyl)sulfonyl]imide, 1-(carboxymethyl)-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, and N-(carboxymethyl)-N-methylpyrrolidinium bis[(trifluoromethyl)sulfonyl]imide. The dissolution process results in the formation of uranyl complexes with zwitterionic carboxylate ligands and bis[(trifluoromethyl)sulfonyl]imide (bistriflimide) counterions. An X-ray diffraction study on single crystals of the uranyl complexes revealed that the crystal structure strongly depends on the cationic core appended to the carboxylate groups. The betainium ionic liquid gives a dimeric uranyl complex, the imidazolium ionic liquid a monomeric complex, and the pyrrolidinium ionic liquid a one-dimensional polymeric uranyl complex. Extended X-ray absorption fine structure measurements have been performed on the betainium uranyl complex. The absorption and luminescence spectra of the uranyl betainium complex have been studied in the solid state and dissolved in water, in acetonitrile, and in the ionic liquid betainium bistriflimide. The carboxylate groups remain coordinated to uranyl in acetonitrile and in betainium bistriflimide but not in water.
[Show abstract][Hide abstract] ABSTRACT: A series of nitrile-functionalized ionic liquids were found to exhibit temperature-dependent miscibility (thermomorphism) with the lower alcohols. Their coordinating abilities toward cobalt(II) ions were investigated through the dissolution process of cobalt(II) bis(trifluoromethylsulfonyl)imide and were found to depend on the donor abilities of the nitrile group. The crystal structures of the cobalt(II) solvates [Co(C(1)C(1CN)Pyr)(2)(Tf(2)N)(4)] and [Co(C(1)C(2CN)Pyr)(6)][Tf(2)N](8), which were isolated from ionic-liquid solutions, gave an insight into the coordination chemistry of functionalized ionic liquids. Smooth layers of cobalt metal could be obtained by electrodeposition of the cobalt-containing ionic liquids.
Chemistry - A European Journal 12/2009; 16(6):1849-58. DOI:10.1002/chem.200901729 · 5.73 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The dissolution process of metal complexes in ionic liquids was investigated by a multiple-technique approach to reveal the solvate species of the metal in solution. The task-specific ionic liquid betainium bis(trifluoromethylsulfonyl)imide ([Hbet][Tf(2)N]) is able to dissolve stoichiometric amounts of the oxides of the rare-earth elements. The crystal structures of the compounds [Eu(2)(bet)(8)(H(2)O)(4)][Tf(2)N](6), [Eu(2)(bet)(8)(H(2)O)(2)][Tf(2)N](6) x 2 H(2)O, and [Y(2)(bet)(6)(H(2)O)(4)][Tf(2)N](6) were found to consist of dimers. These rare-earth complexes are well soluble in the ionic liquids [Hbet][Tf(2)N] and [C(4)mim][Tf(2)N] (C(4)mim = 1-butyl-3-methylimidazolium). The speciation of the metal complexes after dissolution in these ionic liquids was investigated by luminescence spectroscopy, (1)H, (13)C, and (89)Y NMR spectroscopy, and by the synchrotron techniques EXAFS (extended X-ray absorption fine structure) and HEXS (high-energy X-ray scattering). The combination of these complementary analytical techniques reveals that the cationic dimers decompose into monomers after dissolution of the complexes in the ionic liquids. Deeper insight into the solution processes of metal compounds is desirable for applications of ionic liquids in the field of electrochemistry, catalysis, and materials chemistry.
Chemistry - A European Journal 02/2009; 15(6):1449-61. DOI:10.1002/chem.200801418 · 5.73 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The ionic liquid (2-hydroxyethylammonium)trimethylammonium) bis(trifluoromethylsulfonyl)imide (choline bistriflimide) was obtained as a supercooled liquid at room temperature (melting point=30 degrees C). Crystals of choline bistriflimide suitable for structure determination were grown from the melt in situ on the X-ray diffractometer. The choline cation adopts a folded conformation, whereas the bistriflimide anion exhibits a transoid conformation. The choline cation and the bistriflimide anion are held together by hydrogen bonds between the hydroxyl proton and a sulfonyl oxygen atom. This hydrogen bonding is of importance for the temperature-dependent solubility properties of the ionic liquid. Choline bistriflimide is not miscible with water at room temperature, but forms one phase with water at temperatures above 72 degrees C (equals upper critical solution temperature). 1H NMR studies show that the hydrogen bonds between the choline cation and the bistriflimide anion are substantially weakened above this temperature. The thermophysical properties of water-choline bistriflimide binary mixtures were furthermore studied by a photopyroelectric technique and by adiabatic scanning calorimetry (ASC). By photothermal analysis, besides highly accurate values for the thermal conductivity and effusivity of choline bistriflimide at 30 degrees C, the detailed temperature dependence of both the thermal conductivity and effusivity of the upper and lower part of a critical water-choline bistriflimide mixture in the neighborhood of the mixing-demixing phase transition could be determined with high resolution and accuracy. Together with high resolution ASC data for the heat capacity, experimental values were obtained for the critical exponents alpha and beta, and for the critical amplitude ratio G+/G-. These three values were found to be consistent with theoretical expectations for a three dimensional Ising-type of critical behavior of binary liquid mixtures.
The Journal of Physical Chemistry B 02/2009; 113(5):1429-37. DOI:10.1021/jp808993t · 3.30 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The palladium-catalyzed hydrogenolysis of aromatic ketones to alkylbenzenes was studied in mixtures of ionic liquids to explore the promotional effect of these reaction media. Choline-based ionic liquids displayed complete miscibility with the aromatic ketone substrate at reaction temperature and a clear phase separation of the derived alkylbenzene product at room temperature. Selected ionic liquids were then assessed as reaction media in the hydrogenolysis of aromatic ketones over palladium catalysts. A binary mixture of choline and betainium bis(trifluoromethylsulfonyl)imide ionic liquids resulted in the highest conversion and selectivity values in the hydrogenolysis of acetophenone. At the end of the reaction, the immiscible alkylbenzene separates from the ionic liquid mixture and the pure product phase can be isolated by simple decantation. After optimization of the reaction conditions, high yields (>90 %) of alkylbenzene were obtained in all cases. The catalyst and the ionic liquid could be used at least three times without any loss of activity or selectivity.
[Show abstract][Hide abstract] ABSTRACT: Imidazolium, pyridinium, pyrrolidinium, piperidinium, morpholinium, and quaternary ammonium bis(trifluoromethylsulfonyl)imide salts were functionalized with a carboxyl group. These ionic liquids are useful for the selective dissolution of metal oxides and hydroxides. Although these hydrophobic ionic liquids are immiscible with water at room temperature, several of them form a single phase with water at elevated temperatures. Phase separation occurs upon cooling. This thermomorphic behavior has been investigated by (1)H NMR, and it was found that it can be attributed to the temperature-dependent hydration and hydrogen-bond formation of the ionic liquid components. The crystal structures of four ionic liquids and five metal complexes have been determined.
[Show abstract][Hide abstract] ABSTRACT: The structure of one tautomer (amine form) of cyano-carbamimidic acid ethyl ester or (amino-ethoxy-methylidene)aminoformonitrile (CAS: 13947-84-7) was determined by single crystal X-ray diffraction. Ab initio quantum chemical calculations at the B3LYP, MP2 and G3 levels were performed to investigate the stability and the formation of the different tautomers and conformers. The calculations indicate that the amine form is the more stable tautomer, showing a high degree of electron conjugation. The most stable amine conformer located by the calculations corresponds to the crystallized structure. On the contrary, in the less stable imine form, the conjugation is separated by a N2–C2 single bond.
[Show abstract][Hide abstract] ABSTRACT: The crystal structure of the title compound, (C(6)H(11)N(2))(3)[EuBr(6)], consists of 1-ethyl-3-methyl-imidazolium cations and centrosymmetric octa-hedral hexa-bromido-europate anions. The [EuBr(6)](3-) anions are located at the corners and face-centres of the monoclinic unit cell. Characteristic hydrogen-bonding inter-actions can be observed between the bromide anions and the acidic H atoms of the imidazolium cations.
[Show abstract][Hide abstract] ABSTRACT: The task-specific ionic liquid betainium bis(trifluoromethylsulfonyl)imide, [Hbet][Tf2N], was used to dissolve metal oxides and hydroxides. The crystal structures of the resulting metal betaine bistriflimide complexes exhibit a rich structural variety. A trimeric structure was found for the cobalt(II) compound, [Co3(bet)8(Hbet)2(H2O)2][Tf2N]9[Hbet], a tetrameric structure for the manganese(II) and zinc(II) compound, [Mn4(bet)10(H2O)4][Tf2N]8 and [Zn4(bet)10(H2O)2][Tf2N]8, respectively, a pentameric structure for the nickel(II) compound, [Ni5(bet)12(H2O)6][Tf2N]10, an oxo-hydroxo-cluster formation for the lead(II) compound, [(Pb4O)Pb(OH)(bet)8(Tf2N)3][Tf2N]4·MeOH, and a polymeric structure for the silver(I) compound, [Ag2(bet)2(Tf2N)Ag2(bet)2][Tf2N]3. The zwitterionic nature of the betaine ligand and the weakly coordinating ability of the bis(trifluoromethylsulfonyl)imide [Tf2N]− anion facilitates the incorporation of metal ions into oligonuclear and polynuclear metal complexes.
[Show abstract][Hide abstract] ABSTRACT: The electrical conductivities of 1-alkyl-3-methylimidazolium tetrafluoroborate ionic liquids and of 1-hexyl-3-methylimidazolium ionic liquids with different anions were determined in the temperature range between 123 and 393 K on the basis of dielectric measurements in the frequency range from 1 to 10(7) Hz. Most of the ionic liquids form a glass and the conductivity values obey the Vogel-Fulcher-Tammann equation. The glass transition temperatures are increasing with increasing length of the alkyl chain. The fragility is weakly dependent on the alkyl chain length but is highly sensitive to the structure of the anion.
The Journal of Chemical Physics 03/2008; 128(6):064509. DOI:10.1063/1.2827462 · 2.95 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Choline saccharinate and choline acesulfamate are two examples of hydrophilic ionic liquids, which can be prepared from easily available starting materials (choline chloride and a non-nutritive sweetener). The (eco)toxicity of these ionic liquids in aqueous solution is very low in comparison to other types of ionic liquids. A general method for the synthesis and purification of hydrophilic ionic liquids is presented. The method consists of a silver-free metathesis reaction, followed by purification of the ionic liquid by ion-exchange chromatography. The crystal structures show a marked difference in hydrogen bonding between the two ionic liquids, although the saccharinate and the acesulfamate anions show structural similarities. The optimized structures, the energetics, and the charge distribution of cation-anion pairs in the ionic liquids were studied by density functional theory (DFT) and second-order (Møller-Plesset) perturbation theory calculations. The occupation of the non-Lewis orbitals was considered to obtain a qualitative picture of the Lewis structures. The calculated interaction energies and the dipole moments for the ion pairs in the gas phase were discussed.
The Journal of Physical Chemistry B 06/2007; 111(19):5254-63. DOI:10.1021/jp068446a · 3.30 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Cyclic voltammetry and absorption spectrophotometry were used to examine the complex formation of cobalt (II) in the ionic liquids 1-butyl-3-methylimidazolium chloride ([C(4)mim] Cl) and 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide ([C(4)mim][Tf2N]). In [C(4)mim]Cl, cobalt(II) is complexed as [CoCl4](2-) at CoCl2 concentrations less than 33 mol %. Cyclic voltammograms show that cobalt cannot be electrodeposited at these concentrations. However, cobalt metal can be electrodeposited at CoCl2 concentrations above the threshold concentration of 33 mol %. In the ionic liquid [C(4)mim][Tf2N] there is no threshold CoCl2 concentration for electrodeposition due to the absence of [CoCl4](2-). (C) 2007 The Electrochemical Society.