Solvent-Free Functionalization of Carbon Nanotubes

Abstract
A fundamentally new single-walled and multiwalled carbon nanotube sidewall functionalization technique has been developed in which solvent is not required and the reaction times are greatly shortened (1 h at 60 °C). Exploiting the long linear dimension of the nanotube ropes by macroscopic mechanical deformation, reactive sites are generated merely by mechanically deforming the tubes using a stir bar. This approach eliminates the need for large volumes of solvent (∼2 L/g), which were formerly considered essential due to the insolubility of carbon nanotubes. Using a series of 4-substituted anilines and a nitrite, the aryl diazonium intermediates were generated in situ and permitted to react with the tubes. Raman, IR, and UV spectroscopies, coupled with thermogravimetric analyses and solubility studies, support the assignments.