Influence of Hydrogen Bonding Between Ions of Like Charge on the Ionic Liquid Interfacial Structure at a Mica Surface

Ionic liquids (ILs) have attracted increasing interest in science and technology due to their remarkable properties, which can be tuned via varying ion structures to control the relative strengths of Coulomb interactions, hydrogen bonding (H-bonding) and dispersion forces. Here we use atomic force microscopy (AFM) to probe the interfacial nanostructures of hydroxyl-functionalized ILs at negatively charged mica surfaces. H-bonding between hydroxyl functionalised cations (c-c) produces cation clusters and stronger interfacial nanostructure. H-bond stabilised cation clusters form despite opposing electrostatic repulsions between charge groups, cation – anion (c-a) electrostatic attractions, and (c-a) H-bonds. Comparison of ILs with and without OH functionalised cations shows directional H-bonding enhances interfacial structure more strongly than the dispersion forces between alkyl groups. These findings reveal a new means of controlling IL interfacial nanostructure via H-bonding between like charged ions, wh...