Competitive Coordination of Chloride and Fluoride Anions Towards Trivalent Lanthanide Cations (La and Nd ) in Molten Salts.

Molten salt electrolysis is a vital technique to produce high-purity lanthanide metals and alloys. However, the coordination environments of lanthanides in molten salts, which heavily affect the related redox potential and electrochemical properties, have not been well elucidated. Here, the competitive coordination of chloride and fluoride anions towards lanthanide cations (La and Nd ) is explored in molten LiCl-KCl-LiF-LnCl salts using electrochemical, spectroscopic, and computational approaches. Electrochemical analyses show that significant negative shifts in the reduction potential of Ln occur when F concentration increases, indicating that the F anions interact with Ln via substituting the coordinated Cl anions, and confirm [LnCl F ] (y =3) complexes are prevailing in molten salts. Spectroscopic and computational results on solution structures further reveal the competition between Cl and F anions, which leads to the formation of four distinct Ln(III) species: [LnCl ] , [LnCl F] , [LnCl F ] and [LnCl F ] . Among them, the seven-coordinated [LnCl F ] complex possesses a low-symmetry structure evidenced by the pattern change of Raman spectra. After comparing the polarizing power (Z/r) among different metal cations, it was concluded that Ln-F interaction is weaker than that between transition metal and F ions.