Critical Investigation of Defect Site Functionalization on Single-Walled Carbon Nanotubes

The presence of carboxylated carbonaceous material in nitric acid-treated single-walled carbon nanotube (SWNT) samples has recently brought renewed focus on the processes by which covalent functionalization of such materials are carried out. Using a widely reported 2-step purification/oxidation procedure, we have investigated the effect of basic treatment and solvent washing on the functionalization and final properties and behavior of SWNTs. We have demonstrated, using a number of spectroscopic techniques, that in the absence of NaOH treatment, COOH functionality is introduced directly onto SWNTs, and not only onto carbonaceous material present in the sample. Covalent functionalization of the oxidized materials was also investigated by attachment of a fluorescent probe, and ultimately, whether treated with base or solvent washed, the resulting materials are close to identical with respect to both their appearance and properties. In addition, we have demonstrated that using either of these purification/oxidation strategies, functionalized materials can be produced that still exhibit distinctive optical/electronic properties, as demonstrated by sustained structured spectroscopic absorption and emission features.