Confinement Effect of Sub-nanometer Difference on Melting Point of Ice-Nanotubes Measured by Photoluminescence Spectroscopy.

Melting point is independent of size and shape in bulk materials, but it exhibits a size dependence when the material size is extremely small. In this study, we measured the melting point of water confined in single-walled carbon nanotubes (SWCNTs) with 16 different chiralities, which ranged from 0.95 to 1.26 nm in diameter, and revealed the details of the SWCNT diameter dependence on the melting points. The melting points were probed by utilizing the change of photoluminescence (PL) emission wavelength of SWCNTs, which encapsulated water, and the relation between the emission wavelength, and the water phase was confirmed by first-principles calculations. The periodicity of the melting point variation with SWCNT diameter came from the discrete change of ice-nanotube (ice-NT) diameter, and in addition, even ice-NT with an identical diameter exhibited different melting points due to the slight difference of the inner space size of the encapsulating SWCNTs. The present results agreed with those of the molecular dynamics simulation (Takaiwa, D.; et al., Proc. Natl. Acad. Sci. U.S.A. 2008, 105, 39-43). It was elucidated that the melting point of the nanomaterial changed sensitively to the atomic structure and the confinement space size.