Trace Water Changes Metal Ion Speciation in Deep Eutectic Solvents: Ce3+ Solvation and Nanoscale Water Clustering in Choline Chloride-Urea-Water Mixtures

Eutectic mixtures of choline chloride, urea, and water in deep eutectic solvent (DES)/water molar hydration ratios (w) of 2, 5, and 10, with dissolved cerium salt, were measured using neutron diffraction with isotopic substitution. Structures were modeled using empirical potential structure refinement (EPSR). Ce3+ was found to form highly charged complexes with a mean coordination number between 7 and 8, with the shell containing mostly chloride, followed by water. The shell composition is strongly affected by the molar ratio of dilution, as opposed to the mass or volume fraction, due to the high affinity of Cl- and H2O ligands that displace less favorable interactions with ligands such as urea and choline. The presence of Ce3+ salt disrupted the bulk DES structure slightly, making it more electrolyte-like. The measured coordination shell of choline showed significant discrepancies from the statistical noninteracting distribution, highlighting the nonideality of the blend. Cluster analysis revealed the trace presence of percolating water clusters (25 >= n >= 2) in solvent compositions of 5 and 10w for the first time.

Automated summary

This study investigated the structure of eutectic mixtures of choline chloride, urea, and water in deep eutectic solvent (DES) with the addition of cerium salt. It was found that the presence of cerium salt disrupted the structure of the solvent and made it more electrolyte-like. The coordination shell of choline showed significant differences compared to theoretical models. Additionally, the presence of percolating water clusters was observed in specific molar ratios of the solvent for the first time.