Processing Gray Selenium in Phosphonium-Based Ionic Liquids

Pietsch, Tobias and Blasius, Jan and Richter, Janine and Grasser, Matthias A. and Hollóczki, Oldamur and Wollmann, Philipp and Weidinger, Inez M. and Ruck, Michael and Brunner, Eike (2023) Processing Gray Selenium in Phosphonium-Based Ionic Liquids. INORGANIC CHEMISTRY, 62 (4). pp. 1667-1678. ISSN 0020-1669

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Abstract

The dissolution of gray selenium in tetraalkylphosphonium acetate ionic liquids was investigated by UV−vis, NMR, and Raman spectroscopy as well as quantum chemical calculations and electrochemical methods. Acetate anions and tetraalkylphosphonium cations facilitate the formation and stabilization of oligoselenides Sen 2− and cationic Se species in the ionic liquid phase. Chemical exchange of selenium atoms was demonstrated by variable-temperature 77Se NMR experiments. Additionally, uncharged cycloselenium molecules exist at high selenium concentrations. Upon dilution with ethanol, amorphous red selenium precipitates from the solution. Moreover, crystalline Se1−xTex solid solutions precipitate when elemental tellurium is added to the mixture as confirmed by powder X-ray diffraction and Raman spectroscopy.

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