Journal of Colloid and Interface Science, Vol.591, 38-51, 2021
Nanostructure of a deep eutectic solvent at solid interfaces
Hypothesis: Deep eutectic solvents (DESs) are an attractive class of tunable solvents. However, their uptake for relevant applications has been limited due to a lack of detailed information on their structure-property relationships, both in the bulk and at interfaces. The lateral nanostructure of the DES-solid interfaces is likely to be more complex than previously reported and requires detailed, high resolution investigation. Experiments: We employ a combination of high-resolution amplitude-modulated atomic force microscopy and molecular dynamics simulations to elucidate the lateral nanostructure of a DES at the solid liquid interface. Specifically, the lateral and near-surface nanostructure of the DES choline chloride:glycerol is probed at the mica and highly-ordered pyrolytic graphite interfaces. Findings: The lateral nanostructure of the DES-solid interface is heterogeneous and well-ordered in both systems. At the mica interface, the DES is strongly ordered via polar interactions. The adsorbed layer has a distinct rhomboidal symmetry with a repeat spacing of-0.9 nm comprising all DES species. At the highly ordered pyrolytic graphite interface, the adsorbed layer appears distinctly different, forming an apolordriven row-like structure with a repeat spacing of-0.6 nm, which largely excludes the chloride ion. The interfacial nanostructure results from a delicate balance of substrate templating, liquid-liquid interactions, species surface affinity, and packing constraints of cations, anions, and molecular components within the DES. For both systems, distinct near-surface nanostructural layering is observed, which becomes more pronounced close to the substrate. The surface nanostructures elucidated here significantly expand our understanding of DES interfacial behavior and will enhance the optimization of DES systems for surface-based applications. (c) 2021 Elsevier Inc. All rights reserved.