Crystallization of nanopore-confined imidazolium ionic liquids probed by temperature-resolved <i>in situ</i> grazing-incidence wide angle X-ray scattering (GIWAXS)

The crystallization behavior of ionic liquids (ILs) 1-butyl-3-methylimidazolium [BMIM] hexafluorophosphate [PF₆] and chloride [Cl] is investigated upon confinement in 2.3 or 8.2 nm diameter silica nanopore arrays, along with the effects of covalently modifying the pore walls with 1-(3-trimethoxysilylpropyl)3-methylimidazolium [TMS-MIM]⁺ groups. <i>In situ</i> grazing-incidence wide angle X-ray scattering (GIWAXS) is performed during heating from as low as -110 °C to room temperature. Partially ordered "nanodomains" are observed in both ILs in the bulk molten state, but they are disrupted by nanoconfinement. Melting point depression consistent with capillary effects is observed for [BMIM][PF₆] in 2.3 nm pores. However, the melting point is elevated for [BMIM][PF₆] in 8.2 nm pores, which provide sufficient space to stabilize the crystalline phase. For [BMIM][Cl], crystallization is observed only in 8.2 nm bare silica pores, but the melting point is severely depressed. Tethering with IL-like [TMS-MIM⁺] also promotes the crystallization of [BMIM][PF₆], resulting in elevated melting points. The combined effects of a larger pore size and pore surface tethering on [BMIM][PF₆] result in a single stable crystal phase that persists from -140 °C to 25 °C (<i>vs.</i> the bulk melting point of -11 °C). These results show that when ILs are used in confined systems, complex crystallization behavior can emerge depending on the counterion, pore size, and surface modification that require consideration of ion layering in the confined space in addition to surface free energy effects.