Effect of Hydrogen Bonding between Ions of like Charge on the Boundary Layer Friction of Hydroxy-Functionalized Ionic Liquids

Atomic force microscopy has been used to measure the lubricity of a series of ionic liquids (ILs) at mica surfaces in the boundary friction regime. A previously unreported cation bilayer structure is detected at the IL-mica interface due to the formation of H-bonds between the hydroxy-functionalized cations [(c-c) H-bonds], which enhances the ordering of the ions in the boundary layer and improves the lubrication. The strength of the cation bilayer structure is controlled by altering the strength of (c-c) H-bonding via changes in the hydroxyalkyl chain length, the cation charge polarizability, and the coordination strength of the anions. This reveals a new means of controlling IL boundary nanostructure via H-bonding between ions of the same charge, which can impact diverse applications, including surface catalysis, particle stability, electrochemistry, etc.