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DOE OSTI · 3377283

Anion-dependent phase behavior of methylimidazolium-based ionic liquids mixed with water: Correlation between local molecular structure and mesoscale behaviors

Higgins, William Todd [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0000000237184021)·LaNasa, Jacob Arthur [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0000000336566682)·Williams, Darrick Joseph [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0000000239434696)·Nebgen, Benjamin Tyler [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0000000153103263)·Kim, Kyungtae [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0000000232068494)
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Abstract

The mesoscopic phase behavior of decylmethylimidazolium (C 10 mim) ionic liquids (ILs) bearing three monovalent anions—thiocyanate (SCN − ), nitrate (NO 3 − ), and chloride (Cl − )—mixed with water at relatively high IL contents (50–95 wt%) was investigated. Small-angle and wide-angle X-ray scattering (SAXS/WAXS) were employed to follow the evolution of both local and mesoscale structures across this composition range. In the absence of water, C 10 mimSCN and C 10 mimCl behaved as disordered liquids, whereas C 10 mimNO 3 spontaneously formed a hexagonally ordered cylindrical mesophase and displayed a sticky-solid macroscopic appearance. Upon addition of water, C 10 mimSCN remained a viscous liquid and only weakly ordered lamellar domains were observed. This limited ordering is attributed to the lack of hydrogen bonding and weak interaction energy between SCN − anions and C 10 mim + cations. In contrast, the trigonal-planar NO 3 − and point-like Cl − anions promoted the formation of well-defined hexagonal mesophases up to 35–45 wt% water. The formation of hydrogen bonding of the two anions with imidazolium ring protons likely enabled the creation of compact ion clusters that effectively exclude water molecules from the immediate vicinity of the IL aggregates. These findings demonstrate that the interaction energy between ion pairs dictate IL-water interactions and therefore control the transition from disordered liquids to ordered mesophases in IL/water mixtures with high IL contents. In conclusion, the combined SAXS/WAXS analysis reveals a correlation between local intermolecular structure and the emergence of mesoscopic order, providing a systematic framework for tailoring mesoscale structures in alkylimidazolium-based IL/water systems.

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36 MATERIALS SCIENCEImidazolium ionic liquidsMesophase formationX-ray scattering

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Higgins, William Todd [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0000000237184021), LaNasa, Jacob Arthur [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0000000336566682), Williams, Darrick Joseph [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0000000239434696), Nebgen, Benjamin Tyler [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0000000153103263), Kim, Kyungtae [Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)] (ORCID:0000000232068494). 2026-09-01. Anion-dependent phase behavior of methylimidazolium-based ionic liquids mixed with water: Correlation between local molecular structure and mesoscale behaviors. https://doi.org/10.1016/j.molliq.2026.129778

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