Void-Assisted Ion-Paired Proton Transfer at Water-Ionic Liquid Interfaces.

Abstract

At the water-trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate ([P14,6,6,6 ][FAP]) ionic liquid interface, the unusual electrochemical transfer behavior of protons (H(+) ) and deuterium ions (D(+) ) was identified. Alkali metal cations (such as Li(+) , Na(+) , K(+) ) did not undergo this transfer. H(+) /D(+) transfers were assisted by the hydrophobic counter anion of the ionic liquid, [FAP](-) , resulting in the formation of a mixed capacitive layer from the filling of the latent voids within the anisotropic ionic liquid structure. This phenomenon could impact areas such as proton-coupled electron transfers, fuel cells, and hydrogen storage where ionic liquids are used as aprotic solvents.