The Impact of Water on the Lateral Nanostructure of a Deep Eutectic Solvent-Solid Interface

Deep eutectic solvents (DESs) are tuneable solvents with attractive properties for numerous applications. Their structureproperty relationships are still under investigation, especially at the solid-liquid interface. Moreover, the influence of water on interfacial nanostructure must be understood for process optimization. Here, we employ a combination of atomic force microscopy and molecular dynamics simulations to determine the lateral and surface-normal nanostructure of the DES choline chloride:glycerol at the mica interface with different concentrations of water. For the neat DES system, the lateral nanostructure is driven by polar interactions. The surface adsorbed layer forms a distinct rhomboidal symmetry, with a repeat spacing of similar to 0.9 nm, comprising all DES species. The adsorbed nanostructure remains largely unchanged in 75 mol-% DES compared with pure DES, but at 50 mol-%, the structure is broken and there is a compromise between the native DES and pure water structure. By 25 mol-% DES, the water species dominates the adsorbed liquid layer, leaving very few DES species aggregates at the interface. In contrast, the near-surface surface-normal nanostructure, over a depth of similar to 3 nm from the surface, remains relatively unchanged down to 25 mol-% DES where the liquid arrangement changed. These results demonstrate not only the significant influence that water has on liquid nanostructure, but also show that there is an asymmetric effect whereby water disrupts the nanostructure to a greater degree closer to the surface. This work provides insight into the complex interactions between DES and water and may enhance their optimization for surfacebased applications.