Diameter-dependent hydrophobicity in carbon nanotubesSingle-wall carbon nanotubes (SWCNTs) are a good model system that provides atomically smooth nanocavities. It has been reported that water-SWCNTs exhibit hydrophobicity depending on the temperature T and the SWCNT diameter D. SWCNTs adsorb water molecules spontaneously in their cylindrical pores around room temperature, whereas they exhibit a hydrophilic-hydrophobic transition or wet-dry transition (WDT) at a critical temperature T wd ≈ 220-230 K and above a critical diameter D c ≈ 1.4-1.6 nm. However, details of the WDT phenomenon and its mechanism remain unknown. Here, we report a systematic experimental study involving X-ray diffraction, optical microscopy, and differential scanning calorimetry. It is found that water molecules inside thick SWCNTs (D > D c ) evaporate and condense into ice Ih outside the SWCNTs at T wd upon cooling, and the ice Ih evaporates and condenses inside the SWCNTs upon heating. On the other hand, residual water trapped inside the SWCNTs below T wd freezes. Molecular dynamics simulations indicate that upon lowering T, the hydrophobicity of thick SWCNTs increases without any structural transition, while the water inside thin SWCNTs (D < D c ) exhibits a structural transition, forming an ordered ice. This ice has a well-developed hydrogen bonding network adapting to the cylindrical pores of the SWCNTs. Thus, the unusual diameter dependence of the WDT is attributed to the adaptability of the structure of water to the pore dimension and shape. Published by AIP Publishing.[http://dx
Growing long carbon nanotubes (CNTs) is an important prerequisite for practical applications of CNTs. Although gas-flow-guided chemical vapor deposition can be used to produce millimeter-long CNTs, little is known regarding the associated growth mechanism. In the present work, Raman imaging was employed to characterize individual CNTs grown by the gas flow method, and Raman images of a CNT over 1.6 mm long were obtained. Two radial breathing modes were observed and the associated Raman images exhibited exactly identical distributions, indicating that the long CNT most likely had a double-walled structure, in which the CNT diameter was uniform along the whole length.
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