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The electrochemical behavior and electrodeposition of gallium was studied in a non-aqueous electrolyte comprising of gallium(iii) chloride and 1,2-dimethoxyethane (DME). Electrochemical quartz crystal microbalance (EQCM) and rotating ring disk electrode (RRDE) measurements indicate that reduction of gallium(iii) is a two-step process: first from gallium(iii) to gallium(i), and then from gallium(i) to gallium(0). The morphology and elemental composition of the electrodeposited layer were examined using scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). Metallic gallium was deposited as spheres with diameters of several hundred nanometers that were stacked on top of each other. X-ray photoelectron spectroscopy (XPS) revealed that each gallium sphere was covered by a thin gallium oxide shell. Electrochemical experiments indicated that these oxide layers are electrically conductive, as gallium can be electrodeposited and partially stripped on or from the layer of spheres below. This was further evidenced by simultaneous electrodeposition of gallium and indium, using indium as a tracer. Electrodeposition of gallium from an O2-containing electrolyte resulted in spheres with smaller diameters. This was due to the formation thicker oxide shells, through which diffusion of gallium atoms that were electrodeposited on the surface, was slower. The concentration of gallium adatoms on top of the gallium spheres to form a new sphere therefore reaches the critical concentration for nucleating a new gallium sphere sooner, leading to smaller spheres.
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The electrochemical behavior and electrodeposition of indium was investigated at 26 °C and 160 °C from a solution composed of indium(iii) methanesulfonate and dimethylsulfoxide (DMSO). Indium(iii) methanesulfonate was synthesized from indium(iii) oxide and methanesulfonic acid (MSA). Cyclic voltammetry, quartz crystal microbalance measurements and rotating ring disk electrode experiments indicated that reduction of indium(iii) to both indium(i) and indium(0) occurs. Yet, reduction to metallic indium was found to be the predominant process. Deposited indium could be stripped to indium(i). This unstable species disproportionated to indium(iii) and indium(0), leading to the formation of micron-sized metallic indium particles in the electrolyte. At 26 °C, indium deposited on glassy carbon as smooth, flat films whereas at 160 °C, it deposits as droplets.
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Dynamic TGA studies of phosphonium ionic liquids have reported thermal stabilities of 300 °C or higher for these compounds. This is often an overestimation of the real thermal stability. The chosen technique as well as the experimental parameters can influence the thermal stability. In this paper, the thermal stability of commercially available Cyphos IL 101 is studied. The effect of the nature of the atmosphere (air or inert gas), the purity of the sample, the heating rate and presence of a metal on the short-term and long-term stability of commercial Cyphos IL 101 is investigated. The thermal decomposition products are characterized using thermogravimetric analysis coupled to mass spectrometry (TGA-MS). Impurities present and higher heating rates lead to an under- and overestimation of the thermal stability, respectively. The presence of oxygen leads to a lower thermal stability. In contrast, adding metal chlorides to the ionic liquid causes an increase in the thermal stability. The chloride anions are coordinated to the metal ion, so that the Lewis basicity of the anions is reduced. Also this paper gives insights in the behavior of Cyphos IL 101 at high temperatures, which is of relevance for possible application of this ionic liquid in high-temperature industrial processes.
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A hydrometallurgical process is described for conversion of an aqueous solution of lithium chloride into an aqueous solution of lithium hydroxide via a chloride/hydroxide anion exchange reaction by solvent extraction. The organic phase comprises a quaternary ammonium chloride and a hydrophobic phenol in a diluent. The best results were observed for a mixture of the quaternary ammonium chloride Aliquat 336 and 2,6-di-tert-butylphenol (1:1 molar ratio) in the aliphatic diluent Shellsol D70. The solvent extraction process involves two steps. In the first step, the organic phase is contacted with an aqueous sodium hydroxide solution. The phenol is deprotonated, and a chloride ion is simultaneously transferred to the aqueous phase, leading to in situ formation of a quaternary ammonium phenolate in the organic phase. The organic phase, comprising the quaternary ammonium phenolate, is contacted in the second step with an aqueous lithium chloride solution. This contact converts the phenolate into the corresponding phenol by protonation with water extracted to the organic phase, followed by a transfer of hydroxide ions to the aqueous phase and chloride ions to the organic phase. As a result, the aqueous lithium chloride solution is transformed into a lithium hydroxide solution. The process has been demonstrated in continuous counter-current mode in mixer-settlers. Solid battery-grade lithium hydroxide monohydrate was obtained from the aqueous solution by crystallization or by antisolvent precipitation with isopropanol. The process consumes no chemicals other than sodium hydroxide. No waste is generated, with the exception of an aqueous sodium chloride solution. Supplementary Information: The online version contains supplementary material available at 10.1007/s40831-022-00629-2.
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A solvometallurgical process for the separation of indium(iii) and zinc(ii) from ethylene glycol solutions using the ionic liquid extractants Cyphos IL 101 and Aliquat 336 in an aromatic diluent has been investigated. The speciation of indium(iii) in the two immiscible organic phases was investigated by Raman spectroscopy, infrared spectroscopy, EXAFS and 115In NMR spectroscopy. At low LiCl concentrations in ethylene glycol, the bridging (InCl3)2(EG)3 or mononuclear (InCl3)(EG)2 complex is proposed. At higher lithium chloride concentrations, the first coordination sphere changes to two oxygen atoms from one bidentate ethylene glycol ligand and four chloride anions ([In(EG)Cl4]-). In the less polar phase, indium(iii) is present as a tetrahedral [InCl4]- complex independent of the LiCl concentration. After the number of theoretical stages had been determined using a McCabe-Thiele diagram for extraction by Cyphos IL 101, the extraction and scrubbing processes were performed in lab-scale mixer-settlers to test the feasibility of working in continuous mode. Indium(iii) was extracted quantitatively in four stages, with 19% co-extraction of zinc(ii). The co-extracted zinc(ii) was scrubbed selectively in six stages using an indium(iii) scrub solution. Indium(iii) was recovered from the loaded less polar organic phase as indium(iii) hydroxide (98.5%) by precipitation stripping with an aqueous NaOH solution.
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The electrochemical behaviour and deposition of indium in electrolytes composed of 0.4 mol dm-3 In(Tf2N)3 and 0.4 mol dm-3 InCl3 in the solvents 1,2-dimethoxyethane and poly(ethylene glycol) (average molecular mass of 0.400 kg mol-1, PEG400) was investigated. Indium(i) was identified as the intermediate species that disproportionated to indium(iii) and indium(0) nanoparticles. The presence of nanoparticles was verified by TEM analysis. SEM analysis showed that deposits obtained at room temperature from 1,2-dimethoxyethane were rough, while spherical structures were formed in PEG400 at 160 °C.
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The electrochemical behavior of indium in the ionic liquid trihexyl(tetradecyl)phosphonium chloride (Cyphos IL 101) was studied. Cyphos IL 101 first had to be purified, as the impurities present in commercial Cyphos IL 101 interfered with the electrochemical measurements. Electrochemical deposition of indium metal from this electrolyte occurs without hydrogen evolution, increasing the cathodic current efficiency compared to deposition from water and avoiding porosity within the deposited metal. Indium(iii) is the most stable oxidation state in the ionic liquid. This ion is reduced in two steps, first from indium(iii) to indium(i) and subsequently to indium(0). The high thermal stability of Cyphos IL 101 allowed the electrodeposition of indium at 120 °C and 180 °C. At 180 °C indium was deposited as liquid indium which allows for the easy separation of the indium and the possibility to design a continuous electrowinning process. On molybdenum, indium deposits as liquid droplets even below the melting point of indium. This was explained by the combination of melting point depression and undercooling. The possibility to separate indium from iron and zinc by electrodeposition was tested. It is possible to separate indium from zinc by electrodeposition, but iron deposits together with indium.
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Most metal extraction studies focus on the kinetics, the maximum loading and the extraction equilibrium, while structural information on the extracted complexes has been limited. This paper concerns the nature of the indium(iii) chloride complexes, present in the organic and aqueous phase during the solvent extraction of indium(iii) from an aqueous HCl solution by undiluted ionic liquids Cyphos® IL 101 and Aliquat® 336. In an aqueous HCl solution (0-12 M), indium(iii) exists as octahedral mixed complexes, [In(H2O)6-nCln]3-n (0 ≤ n ≤ 6). EXAFS and 115In NMR were used to characterize these species. The stoichiometric composition of the extracted complexes, which is estimated from viscosity and maximum loading studies and confirmed by EXAFS, is unaffected by the HCl concentration in the aqueous phase. Indium(iii) is present in the ionic liquid phase as the tetrahedral [InCl4]- complex. Based on the speciation results an extraction mechanism is proposed.