Solvent-free derivatization of pristine multi-walled carbon nanotubes with dithiols

We report on direct solvent-free derivatization of pristine multi-walled carbon nanotubes (MWNTs) with aliphatic dithiols (1,4-butanedithiol, 1,6-hexanedithiol and 1,8-octanedithiol), by means of heating at 130–150 °C under reduced pressure. This method requires no additional chemical activation and about 2 h only for completion. Studies by high-resolution transmission electron microscopy and scanning electron microscopy with energy dispersive X-ray spectroscopy showed that dithiol-derivatized MWNTs have a high affinity to ZnCl2 in solution, which covers the nanotubes with a dense amorphous layer. According to PM3 semi-empirical calculations, employing a closed-cap zigzag (10,0) single-walled carbon nanotube (SWNT) model incorporating a Stone-Wales defect, site-specificity of the addition depends on the mutual position of pentagons. If the nanotube contains pyracylene units or Stone-Wales defect, the addition takes place on their 6,6 or 7,7 bonds, respectively, whereas for isolated pentagons, preferential reaction sites are their C–C bonds. Ideal graphene sheet sidewalls with cylindrical curvature are relatively inert (although one cannot discard the possibility to activate the reaction by heating). Dithiol groups introduced in the way proposed can be used as chemical linkers for anchoring metal complexes and nanoparticles to carbon nanotubes, attaching SWNTs to gold tips for atomic force and scanning tunneling microscopy, and potentially for adsorption and concentration of trace metal ions.