Processing Gray Selenium in Phosphonium-Based Ionic Liquids

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 Sen2- 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.

Automated summary

The dissolution of gray selenium in tetraalkylphosphonium acetate ionic liquids was studied using various spectroscopic and analytical techniques. The presence of acetate anions and tetraalkylphosphonium cations facilitated the formation and stabilization of oligoselenides and cationic Se species in the ionic liquid phase. Chemical exchange of selenium atoms was observed, and uncharged cycloselenium molecules were identified at high selenium concentrations. Upon dilution with ethanol, amorphous red selenium precipitated from the solution, while the addition of elemental tellurium resulted in the precipitation of crystalline Se1-xTex solid solutions.