Temperature-Dependent Surface Enrichment Effects in Binary Mixtures of Fluorinated and Non-Fluorinated Ionic Liquids

Using angle-resolved X-ray photoelectron spectroscopy (ARXPS), we investigate the topmost nanometers of various binary ionic liquid (IL) mixtures at different temperatures in the liquid state. The mixtures consist of ILs with the same [PF₆ ]^- anion but two different cations, namely 3-methyl-1-(3,3,4,4,4-pentafluorobutyl)imidazolium hexafluorophosphate, [PFBMIm][PF₆ ], and 1-butyl-3-methylimidazolium hexafluorophosphate, [C₄ C₁ Im][PF₆ ], with 10, 25, 50 and 75 mol % content of [PFBMIm][PF₆ ]. We observe a preferential enrichment of the fluorinated chain in the topmost layer, relative to the bulk composition, which is most pronounced for the lowest content of [PFBMIm][PF₆ ]. Upon cooling the mixtures stepwise from 95 °C until surface charging effects in XPS indicate solidification, we observe a pronounced increase in surface enrichment of the fluorinated chain with decreasing temperature in the liquid state. In contrast to the mixtures with lower [PFBMIm][PF₆ ] contents, cooling the 75 mol % mixture additionally shows an abrupt decrease of the fluorinated chain signal before complete solidification occurs, which is assigned to partial precipitation effects.