We have found a method for a diameter-selective removal of metallic single-walled carbon nanotubes (m-SWCNTs) from semiconducting (s-) ones by stirring or sonicating SWCNT powder in tetramethylene sulfone (TMS)/chloroform solution with nitronium hexafluoroantimonate (NO2SbF6: NHFA) and nitronium tetrafluoroborate (NO2BF4: NTFB). Positively charged nitronium ions (NO2+) were intercalated into nanotube bundles, where the intercalation was promoted also by the counterions. Nitronium ions selectively attacked the sidewall of the m-SWCNTs due to the abundant presence of electron density at the Fermi level, thus yielding stronger binding energy as compared to the counterpart s-SWCNTs. The s-SWCNTs were left on the filter after filtration, whereas the m-SWCNTs were disintegrated and drained away as amorphous carbons. The effectiveness of removing m-SWCNTs was confirmed by the resonant Raman spectra and absorption spectra.
We explore the importance of the size and position of nanoholes on the electrochemical performance of single-walled carbon nanohorn (SWCNH)-based supercapacitors using an ionic liquid electrolyte. The oxidized sample at 673 K showed a low specific capacitance per unit of internal specific surface area (4.0 μF cm −2 ), as the nanoholes created on the tips of SWCNHs via a selective chemical attack are too small to introduce electrolyte ions. For a sample oxidized at 723 K, the enlarged diameter of the nanoholes on the tips allows electrolyte ions to penetrate into the internal spaces of the SWCNHs, thereby resulting in a 2-fold capacitance improvement (8.6 μF cm −2 ). However, the abrupt decrease in the capacitance of the oxidized SWCNHs at 823 K (3.8 μF cm −2 ) can be explained by the selective formation of nanoholes on the sidewalls of the SWCNHs, where the small interstitial pores restrict ion diffusion to deeply positioned nanoholes on the sidewalls of the SWCNHs. Our study clearly reveals that the size and position of nanoholes with regard to ion accessibility are crucial factors to improve the capacitive performance of SWCNH-based supercapacitors.
Carbon nanotubes have shown great potential as conductive fillers in various composites, macro-assembled fibers, and transparent conductive films due to their superior electrical conductivity. Here, we present an effective defect engineering strategy for improving the intrinsic electrical conductivity of nanotube assemblies by thermally incorporating a large number of boron atoms into substitutional positions within the hexagonal framework of the tubes. It was confirmed that the defects introduced after vacuum ultraviolet and nitrogen plasma treatments facilitate the incorporation of a large number of boron atoms (ca. 0.496 atomic %) occupying the trigonal sites on the tube sidewalls during the boron doping process, thus eventually increasing the electrical conductivity of the carbon nanotube film. Our approach provides a potential solution for the industrial use of macro-structured nanotube assemblies, where properties, such as high electrical conductance, high transparency, and lightweight, are extremely important.
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