Spectroscopic Study into Lanthanide Speciation in Deep Eutectic Solvents

[Image: see text] Deep eutectic solvents are a new class of green solvents that are being explored as an alternative for used nuclear fuel and critical material recycling. However, there is a paucity of knowledge regarding metal behavior in them. This paper explores the underlying chemistry of rare-earth elements in choline chloride-based deep eutectic solvents by using a multi-technique spectroscopic methodology. Results show that speciation is highly dependent on the choice of the hydrogen-bond donor. Collected EXAFS data showed Ln(3+) coordination with ethylene glycol and urea in their respective solvents and coordination with chloride in the lactic acid system. Generalized coordination environments were determined to be [LnL(4–5)], [LnL(7–10)], and [LnL(5–6)] in the ethylene glycol, urea, and lactic acid systems, respectively. Collected UV/vis spectra for Nd(3+) and Er(3+) showed variations with changing solvents, showing that Ln–Cl interactions do not dominate in these systems. Luminescence studies were consistent, showing varying emission spectra with varying solvent systems. The shortest luminescent lifetimes were observed in the choline chloride–ethylene glycol deep eutectic solvent, suggesting coordination through O–H groups. Combining all collected data allowed Eu(3+) coordination geometries to be assigned.