Electrochemical and spectroscopic study of Eu(III)/Eu(II) couple in the 1-ethyl-3-methylimidazolium bis(trifluromethanesulfonyl)imide ionic liquid

Abstract

Ionic liquids (ILs) are molten salts composed of an organic cation that are liquid below 100 °C. They demonstrate unique physico-chemical properties such as good conductivity, negligible vapor pressure and non-flammability. As a consequence, they are often regarded as green solvents and could become an alternative to the use of both high-temperature molten salts and volatile organic solvents in rare-earth elements processing and recycling. The diversity of interactions existing in an ionic liquid allows the solubilization of both polar and apolar compounds. Moreover, coordinating functions on their composing ions can lead to stabilization of some species. For instance, in non-aqueous media, europium exists in the (II) oxidation state which is not stable in aqueous solutions. Understanding the mechanism of Eu(III) electrochemical reduction to Eu(II) and the stabilization of Eu(II) species in IL media could be of major interest for the development of innovative recycling processes. Using transient electrochemistry and UV-Vis spectroscopy we could get valuable information on the redox behavior of the Eu(III)/(II) couple in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([EMIm][NTf2]). Reduction of Eu(III) to Eu(II) and stability of Eu(II) was also studied thanks to a XAS-spectro-electrochemistry set up used to follow in situ the evolution of the XANES spectrum around the L3 edge of Eu during electrolysis.