Self-assembly of ionic and non-ionic surfactants in type IV cerium nitrate and urea based deep eutectic solvent

Understanding and manipulating micelle morphology are key to exploiting surfactants in various applications. Recent studies have shown surfactant self-assembly in a variety of Deep Eutectic Solvents (DESs) where both the nature of surfactants and the interaction of the surfactant molecule with the solvent components influence the size, shape, and morphology of the micelles formed. So far, micelle formation has only been reported in type III DESs, consisting solely of organic species. In this work, we have explored the self-assembly of cationic surfactant dodecyl trimethylammonium nitrate/bromide (C₁₂TANO₃/C₁₂TAB), anionic surfactant sodium dodecyl sulfate (SDS), and non-ionic surfactants hexaethylene glycol monododecyl ether (C₁₂EO₆) and octaethylene glycol monohexadecyl ether (C₁₆EO₈) in a type IV DES comprising metal salt, cerium (III) nitrate hexahydrate, and a hydrogen bond donor, urea, in the molar ratio 1:3.5. C₁₂TANO₃, C₁₂TAB, C₁₂EO₆, and C₁₆EO₈ form spherical micelles in the DES with the micelle size dependent on both the surfactant alkyl chain length and the head group, whereas SDS forms cylindrical micelles. We hypothesize that the difference in the micelle shape can be explained by counterion stabilization of the SDS headgroup by polycations in the DES compared to the nitrate/bromide anion interaction in the case of cationic surfactants or molecular interaction of the urea and the salting out effect of (CeNO₃)₃ in the DES on the alkyl chains/polyethoxy headgroup for non-ionic surfactants. These studies deepen our understanding of amphiphile self-assembly in this novel, ionic, and hydrogen-bonding solvent, raising the opportunity to use these structures as liquid crystalline templates to generate porosity in metal oxides (ceria) that can be synthesized using these DESs.