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The Influence of Silica Nanoparticles on Ionic Liquid Behavior: A Clear Difference between Adsorption and Confinement
Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, China
Graduate University of Chinese Academy of Sciences, Beijing 100049, China
* Author to whom correspondence should be addressed.
Received: 12 August 2013; in revised form: 26 September 2013 / Accepted: 29 September 2013 / Published: 18 October 2013
Abstract: The phase behaviors of ionic liquids (ILs) confined in nanospace and adsorbed on outer surface of nanoparticles are expected to be different from those of the bulk. Anomalous phase behaviors of room temperature ionic liquid tributylhexadecylphosphonium bromide (P44416Br) confined in ordered mesoporous silica nanoparticles with average pore size 3.7 nm and adsorbed on outer surface of the same silica nanoparticles were reported. It was revealed that the melting points (Tm) of confined and adsorbed ILs depressed significantly in comparison with the bulk one. The Tm depressions for confined and adsorbed ILs are 8 °C and 14 °C, respectively. For comparison with the phase behavior of confined P44416Br, 1-butyl-3-methylimidazolium bromide (BmimBr) was entrapped within silica nanopores, we observed an enhancement of 50 °C in Tm under otherwise similar conditions. The XRD analysis indicates the formation of crystalline-like phase under confinement, in contrast to the amorphous phase in adsorbed IL. It was confirmed that the behavior of IL has clear difference. Moreover, the complex π-π stacking and H-bonding do not exist in the newly proposed phosphonium-based IL in comparison with the widely studied imidazolium-based IL. The opposite change in melting point of P44416Br@SiO2 and BmimBr@SiO2 indicates that the cationic species plays an important role in the variation of melting point.
Keywords: confinement; adsorption; ionic liquid; melting point; phase behavior
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Wang, Y.; Li, C.; Guo, X.; Wu, G. The Influence of Silica Nanoparticles on Ionic Liquid Behavior: A Clear Difference between Adsorption and Confinement. Int. J. Mol. Sci. 2013, 14, 21045-21052.
Wang Y, Li C, Guo X, Wu G. The Influence of Silica Nanoparticles on Ionic Liquid Behavior: A Clear Difference between Adsorption and Confinement. International Journal of Molecular Sciences. 2013; 14(10):21045-21052.
Wang, Yaxing; Li, Cheng; Guo, Xiaojing; Wu, Guozhong. 2013. "The Influence of Silica Nanoparticles on Ionic Liquid Behavior: A Clear Difference between Adsorption and Confinement." Int. J. Mol. Sci. 14, no. 10: 21045-21052.