We present the first systematic study of the influence of temperature on the degree of surface enrichment of 1-alkyl-3-methylimidazolium-based ionic liquids (ILs). Using angle-resolved X-ray photoelectron spectroscopy, we demonstrate that the degree of surface enrichment strongly decreases with increasing temperature for all the studied ILs. For ILs with the same cation, but different anions, [C8C1Im]Br, [C8C1Im][TfO] and [C8C1Im][Tf2N], no significant differences of the temperature-induced partial loss of surface enrichment are found. Measurements for [C4C1Im][TfO], [C8C1Im][TfO] and [C18C1Im][TfO] indicate a small effect of the chain length. For [C18C1Im][TfO], a continuous decrease of alkyl surface enrichment is found with increasing temperature, with no abrupt changes at the phase-transition temperature from the smectic A to the isotropic phase, indicating that the surface enrichment is not affected by this phase transition.
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