⎯Adsorbents based on silica chemically modified by sulfur-containing groups (dithiocarbamate, thiodiazolethiol, mercaptophenyl, and aminobenzothiazole) quantitatively extract (recovery ≥99%) platinum(IV) from solutions ranging from 4 M HCl to pH 6. Under the conditions of the adsorption separation of platinum(IV), rhenium(VII) is not extracted and remains in the solution. The subsequent quantitative (98-99%) adsorption of rhenium(VII) is achieved in the presence of a 1000-fold excess of tin(II) chloride. Adsorption on the surface of adsorbents leads to the formation of platinum(II) complexes with sulfur-containing groups, luminescent at 77 K on irradiation with UV light. The luminescence spectra of surface platinum(II) complexes are located in the region of 550-700 nm. In the adsorption of rhenium(III) in the presence of tin(II) chloride, intensely colored brown complexes of rhenium formed on the surface of adsorbents. Electron paramagnetic resonance showed that, in the surface complexes, rhenium is in the oxidation state 2+. Silicas chemically modified by sulfur-containing groups were used in the development of procedures for the sequential isolation and determination of platinum and rhenium in solutions after the decomposition of aluminum-platinum-rhenium catalysts.
Silicas chemically modified with a number of sulfur-containing groups (mercaptopropyl, mercaptophenyl, dipropyl disulfide, thiadiazole thiol, dithiocarbamate and thiourea derivatives) were proposed for the separation and preconcentration of precious metals. These adsorbents quantitatively extracted precious metals from 0.5 to 4 M solutions of hydrochloric acid. It allowed their separation from high concentrations of non-ferrous, alkaline earth, alkali and some other related metals. The selectivity of separation of kinetically labile precious metal ions in ligand substitution reactions from kinetically inert ones depended on the nature of sulfur atom within the functional group of adsorbents and increased when passing from thione to thiol sulfur. Approaches for the preconcentration of precious metals using silicas chemically modified with sulfur-containing groups prior to their AAS, ICP-OES, and ICP-MS determination in ores, concentrates and their processing products were proposed. The correctness of the developed methods was confirmed by the analysis of certified reference materials.
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