Effect of Surface Chemistry on the Electrical Double Layer in a Long-Chain Ionic Liquid.

Room temperature ionic liquids (ILs) can create a strong accumulation of charges at solid interfaces by forming a very thin and dense electrical double layer (EDL). The structure of this EDL has important consequences in numerous applications involving ILs, for example, in supercapacitors, sensors, and lubricants, by impacting the interfacial capacitance, the charge carrier density of semiconductors, as well as the frictional properties of the interfaces. We have studied the interfacial structure of a long chain imidazolium-based IL (1-octyl-3-methylimidazolium dicyanamide) on several substrates: mica, silica, silicon, and molybdenum disulfide (MoS2), using atomic force microscopy (AFM) experiments and molecular dynamics (MD) simulations. We have observed 3 types of interfacial structures for the same IL, depending on the chemistry of the substrate and the water content, showing that the EDL structure is not an intrinsic property of the IL. We evidenced that at a low water content, neutral and apolar (thus hydrophobic) substrates promote a thin layer structure, where the ions are oriented parallel to the substrate and cations and anions are mixed in each layer. In contrast, a strongly charged (thus hydrophilic) substrate yields an extended structuration into several bilayers, while a heterogeneous layering with loose bilayer regions was observed on an intermediate polar and weakly charged substrate and on an apolar one at a high bulk water content. In the latter case, water contamination favors the formation of bilayer patches by promoting the segregation of the long chain IL into polar and apolar domains.

Effect of ion structure on the physicochemical properties and gas absorption of surface active ionic liquids.

Surface active ionic liquids (SAILs) combine useful characteristics of both ionic liquids (ILs) and surfactants, hence are promising candidates for a wide range of applications. However, the effect of SAIL ionic structures on their physicochemical properties remains unclear, which limits their uptake. To address this knowledge gap, in this work we investigated the density, viscosity, surface tension, and corresponding critical micelle concentration in water, as well as gas absorption of SAILs with a variety of cation and anion structures. SAILs containing anions with linear alkyl chains have smaller molar volumes than those with branched alkyl chains, because linear alkyl chains are interdigitated to a greater extent, leading to more compact packing. This interdigitation also results in SAILs being about two orders of magnitude more viscous than comparable conventional ILs. SAILs at the liquid-air interface orient alkyl chains towards the air, leading to low surface tensions closer to n-alkanes than conventional ILs. Critical temperatures of about 900 K could be estimated for all SAILs from their surface tensions. When dissolved in water, SAILs adsorb at the liquid-air interface and lower the surface tension, like conventional surfactants in water, after which micelles form. Molecular simulations show that the micelles are spherical and that lower critical micelle concentrations correspond to the formation of aggregates with a larger number of ion pairs. CO2 and N2 absorption capacities are examined and we conclude that ionic liquids with larger non-polar domains absorb larger quantities of both gases.