This Review deals with the evolving field of polyhalogen chemistry, specifically polyhalogen anions (polyhalides). In addition to a historical outline, current progress in synthetic approaches towards the formation of polyfluorides, polychlorides, polybromides, and polyinterhalides is also illustrated. The structural diversity of polyhalides has substantially increased in the past decade, especially for polychlorides and polybromides, which are commonly characterized by single-crystal X-ray diffraction, Raman spectroscopy, and quantum-chemical calculations. Polyfluorides have been examined by sophisticated state-of-the-art quantum-chemical calculations and investigated spectroscopically in noble gas matrix-isolation experiments under cryogenic conditions at 4 K. The bonding in such polyhalide systems is also discussed. The last Section deals with applications of polyhalides in halogenation reactions and electrochemistry as well as their use as reactive ionic liquids, emphasizing the promising future of polyhalogen chemistry.

Polyhalogen and Polyinterhalogen Anions from Fluorine to Iodine.

Dissolution of metals in organic solvents is relevant to various application fields, such as metal extraction from ores or secondary resources, surface etching or polishing of metals, direct synthe...

Oxidative Dissolution of Metals in Organic Solvents.

In the past decades, the demand for platinum group metals (PGMs) has increased rapidly in various applications such as electronics, chemical engineering, biomedical devices, and automotive catalytic converters. Recovery of PGMs from secondary resources is necessary for addressing the supply issues. The migration of PGMs from solid to liquid streams is irreplaceable for achieving high-purity products. Hence, it is a meaningful issue to reduce resource depletion and avoid environmental pollution during separation processes. This paper systematically reviews various improvements and new technologies for the separation and purification of PGMs, including solvent extraction, membranes separation, supercritical fluids, solid-phase extraction, photoreduction, and electrochemical methods. The separation mechanism and optimized process parameters are summarized. Particularly, the advantages, challenges, and perspective are highlighted in terms of commercial applications. This study aims to present the current research for scholars, and to identify a promising PGMs separation method that is safe and effective. Finally, several recommendations have been proposed for the further promotion of separation technologies.

Separation and purification of platinum group metals from aqueous solution: Recent developments and industrial applications

Among ionic liquids, phosphonium-based ionic liquids (PILs) are quite elegant. These categories of ionic liquids represent some merits over other types of ionic liquids such as imidazolium- and pyridinium-based ionic liquids. PILs have more thermal and chemical stability than other reported ILs. These influential characteristics connected with PILs make them as potential structures for varied applications in academic and industrial processes. In recent years, however, PILs become popular because of relatively low cost of their synthesis (the rate of phosphonium salt formation is faster than those of nitrogen-based salts, implying higher productivity and lower cost in industrial manufacturing of PILs) as well as their good thermal stability, beneficial for high-temperature operation. Room temperature ionic liquids (RTILs) have numbers of unique applications in electrochemical systems and among them, phosphonium room temperature ionic liquids (PRTILs) have been increasing for their considerable advantages such as chemical and thermal stabilities, relatively low viscosities and high conductivities when compared to the corresponding ammonium RTILs. PRTILs are yummy electrolysis solutions because of their wide electrochemical window. Determination of the electrochemical stability of the PRTILs is important for detection and application of these ionic salts as electrolytes in electrochemistry. In order to evaluate electrochemical stability of the phosphonium RTILs, various voltammetric techniques such as cyclic voltammetry, linear sweep voltammetry and square wave voltammetry have been used. PRTILs characterized by a wide electrochemical window have been regarded as attractive candidates for lithium-battery electrolytes because of their stability and safety aspects. Contrary to what is seen in conventional organic solvents, superoxide is stable in ionic liquids. PILs are an unprecedented class of electrolytes that can support the electrochemical generation of a stable superoxide ion and can offer many advantages such as low combustibility, ionic conductivity, low volatility and a wide electrochemical window. PILs have been intensively developed as new electrolytic mediator for various electrochemical devices such as supercapacitors and lithium-ion batteries. There is also a growing interest for their use in separation processes including metal ions extraction, extractive desulfurization, gas adsorption and dissolution or extraction of biologically relevant compounds and materials. In mentioned processes and other applications where PIL is the solvent, of particular interest are physicochemical properties (e.g., viscosity, density, surface tension, solubility, polarity and so on). Moreover, the quantum chemical method is invoked to interpret superior properties of PILs. Experimental works have also satisfied that the PILs fulfill the necessary requirement of being a good inhibitor of metal corrosion in different media because of surface active properties. Owning to special physicochemical properties, the PILs are emerging as possible candidates to improve surfactant-enhanced oil recovery methods. Because they have also shown great importance in a vast number of industrial and pharmaceutical applications, such as lubricants, electrolytes, or solvents/catalysts for organic reactions, ecotoxicity of these ILs was studied for environmental and human health risks assessments. PILs have been used as efficient solvents and/or catalysts for synthesis of various kinds of organic compounds. This review article presents an excellent puzzle that each of its pieces lead to the rational design, synthesis and applications of novel and task-specific PILs as multi-purpose materials.

Applications of phosphonium-based ionic liquids in chemical processes

Recycling of samarium–cobalt (SmCo) magnets is essential due to the limited resources of the mentioned metals and their high economic importance. The ionic liquid (IL) trihexyltetradecylphosphonium trichloride, [P666,14][Cl3], which can safely store chlorine gas in the form of the trichloride anion, was used as an oxidizing solvent for the recovery of metals from spent SmCo magnets. The dissolution was studied considering various mixtures of the ILs [P666,14][Cl3] and [P666,14]Cl, solid-to-liquid ratios and different temperatures. The results showed that the maximum capacity of [P666,14][Cl3] for SmCo magnets was 71 ± 1 mg/g of [P666,14][Cl3], in the presence of an extra source of coordinating chloride ions. The maximum loading of the IL could be reached within 3 h at 50 °C. Four stripping steps effectively removed all metals from the loaded IL, where sodium chloride solution (3 mol L–1), twice water and ammonia solution (3 mol L–1) were used consecutively as the stripping solvents. The regenerated IL sho...

Metal Recovery from Spent Samarium-Cobalt Magnets Using a Trichloride Ionic Liquid.

Trihalide ionic liquids as non-volatile oxidizing solvents for metals

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Trihalide ionic liquids as non-volatile oxidizing solvents for metals