Transport Properties and Local Structure of an Imidazole/Protic Ionic Liquid Mixture Confined in the Mesopores of Hydrophobic Silica
Journal article, 2021
The local structure and the molecular dynamics of an imidazole/protic ionic liquid mixture have been investigated while confined in only ca. 5 nm mesopores of silica particles. The walls of the silica pores were functionalized with trioctyl groups to ensure a hydrophobic character, and a series of hybrid materials with varying liquid-to-silica ratios were investigated. Results from vibrational spectroscopy (both Raman and infrared) indicate that the local ion-ion interactions as well as the nature of hydrogen bonds inside the nanopores are not significantly different from the case of the bulk liquid mixture. Nevertheless, the ionic conductivity decreases rapidly and monotonically with decreasing amount of liquid, while the self-diffusion coefficients measured by pulsed field gradient nuclear magnetic resonance (NMR) show a distinct dependence on composition. The population of molecules outside the particles seems to contribute with an enhanced diffusivity, while the molecules inside the mesopores diffuse at a rate comparable to that observed in the bulk liquid. In addition, when experimentally possible, we have measured higher diffusivities for the exchangeable -NH proton than for any other molecular species, which is indicative of a decoupled proton motion. Results from X-ray scattering, employed to elucidate the local molecular structure, reveal an additional feature characteristic of the nanoconfined state, which is associated with a real space distance of about 3.5 nm. This distance describes a specific molecular organization inside the mesopores and may reflect the formation of a monolayer of the octyl-imidazolium cations self-assembled at the hydrophobic silica surface. Such a local structure would favor the localization of charges, including the exchangeable protons. In addition, the analysis of molar conductivity suggests that a major problem with a low pore filling is the emergence of discontinuities throughout the liquid phase.