The local structures between nano-TiO2 and 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMI+TFS–) and 1-butyl-3-methylimidazolium trifluoromethanesulfonate (BMI+TFS–) were investigated using high-pressure infrared spectroscopy. No significant changes in C–H spectral features of EMI+TFS– were observed in the presence of nano-TiO2 under ambient pressure. As the EMI+TFS–/nano-TiO2 mixture was compressed to 0.3 GPa, the imidazolium C–H absorptions became two sharp bands at 3108 and 3168 cm–1, respectively, and the alkyl C–H stretching absorption exhibits a new band at 3010 cm–1 associated with a weaker band at 3028 cm–1. It appears that pressure stabilizes the isolated conformations due to pressure-enhanced imidazolium C–H–-nano-TiO2 interactions. Our results also reveal that alkyl C–H groups play non-negligible roles at the conditions of high pressures. The results of BMI+TFS–/nano-TiO2 are remarkably different from what is revealed for EMI+TFS–/nano-TiO2. The spectral features and band frequencies of BMI+TFS–/nano-TiO2 are almost identical to those of pure BMI+TFS– under various pressures. This study demonstrates that changes to the alkyl chain length of the cation could be made to control the order and strength of ionic liquid/nano-TiO2 interactions.
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