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Atomic force microscopy (AFM), density functional theory (DFT) calculations, and contact angle measurements have been used to investigate the liquid–highly ordered pyrolytic graphite (HOPG) electrode interface for three deep eutectic solvents (DESs) as a function of applied potential. The DESs examined are 1:2 mixtures of choline chloride and urea (ChCl:urea), choline chloride and ethylene glycol (ChCl:ethylene glycol), and choline chloride and glycerol (ChCl:glycerol). DFT calculations reveal that in all cases the molecular component is excluded from the graphite interface at all potentials, while chloride and choline are attracted into the Stern layer at positive and negative potentials, respectively. AFM force curves confirm these trends and also show that the first near surface liquid layer in contact with the Stern layer is rich in the molecular component. The extent of near surface layering increases with potential and the hydrogen bonding capacity of the molecular component. The variation in the macroscopic contact angle with potential is consistent with changes in the Stern layer composition.

Approximate partial phase diagrams for nine amphiphile-protic ionic liquid (PIL) systems have been determined by synchrotron source small angle X-ray scattering, differential scanning calorimetry and cross polarised optical microscopy. The binary phase diagrams of some common cationic (hexadecyltrimethyl ammonium chloride, CTAC, and hexadecylpyridinium bromide, HDPB) and nonionic (polyoxyethylene (10) oleyl ether, Brij 97, and Pluronic block copolymer, P123) amphiphiles with the PILs, ethylammonium nitrate (EAN), ethanolammonium nitrate (EOAN) and diethanolammonium formate (DEOAF), have been studied. The phase diagrams were constructed for concentrations from 10 wt% to 80 wt% amphiphile, in the temperature range 25 °C to >100 °C. Lyotropic liquid crystalline phases (hexagonal, cubic and lamellar) were formed at high surfactant concentrations (typically >50 wt%), whereas at <40 wt%, only micelles or polydisperse crystals were present. With the exception of Brij 97, the thermal stability of the phases formed by these surfactants persisted to temperatures above 100 °C. The phase behaviour of amphiphile-PIL systems was interpreted by considering the PIL cohesive energy, liquid nanoscale order, polarity and ionicity. For comparison the phase behaviour of the four amphiphiles was also studied in water.