Surfactant-mediated ion exchange and charge reversal at ionic liquid interfaces

Room-temperature ionic liquids (ILs) exhibit a unique set of properties due to their charged character, presenting opportunities for numerous applications. Here, we show that the combination of charged surfactants with ILs leads to rich interfacial behavior due to the interplay between electrostatic and surface forces. Using traditional measures of surface activity and X-ray photoelectron spectroscopy (XPS), we find that sodium alkyl sulfates and alkyl trimethylammonium bromides are, indeed, surface-active at the air-IL interfaces of both [EMIM][EtSO(4)] and [BHEDMA][MeSO(3)]. XPS also reveals that surfactant counterions readily dissociate into the bulk, which when combined with the surfactant surface activity has striking consequences. We find that ion exchange occurs between surfactants and like-charged IL ions, with the greatest exchange for short surfactant alkyl chains. The initial negative surface charge of neat [EMIM][EtSO(4)] can be switched to positive by the addition of alkyl trimethylammonium bromides, with the effect most pronounced at short chain lengths. By contrast, the surface charge of [BHEDMA][MeSO(3)] is largely unaffected by the added surfactants, suggesting a key role for the strength of ion-pairing within the IL. The results here illustrate a simple but effective means of manipulating IL interfacial properties.