Selective removal of metallic single-walled carbon nanotubes with small diameters by using nitric and sulfuric acids

Coexistence of metallic and semiconducting carbon nanotubes has often been a bottleneck in many applications and much fundamental research. Single-walled carbon nanotubes (SWCNTs) were dissolved in HNO3/H2SO4 mixture to confirm differing reactivity between metallic (m) and semiconducting (s) SWCNTs. With HNO3/H2SO4 treatment, s-SWCNTs remained intact, while m-SWCNTs were completely removed for SWCNTs with small diameters less than 1.1 nm, which was confirmed by resonant Raman and optical absorption spectra. We also showed that nitronium ions (NO2+) dissolved in the HNO3/H2SO4 solution could preferably attack the m-SWCNTs, which was supported by our theoretical calculation. This clear selectivity can be explained by the preferential adsorption of positively charged NO2+ on m-SWCNTs due to more available electron densities at the Fermi level in the m-SWCNTs. We report for the first time a selective removal of small-diameter m-SWCNTs by using HNO3/H2SO4 solution, which presented a striking contrast to the diameter-selective removal of SWCNTs by oxidative etching reported previously.