Chlorination of carbon nanotubes

Abstract

We report ab initio density functional theory calculations for chlorinated single-wall carbon nanotubes and investigate the atomic structure, energetics, and electronic structure of the chlorinated nanotubes, as well as the energetics of the desorption reaction. We find that the Cl atoms should be adsorbed in pairs and thus focus on doubly chlorinated nanotubes. Using the terminology of arene substitution patterns, ortho and para configurations are the most stable. The physisorption is preferable to the chemisorption in large-diameter nanotubes. The impurity states appear near the Fermi level E-F in the electronic structure and may alter the electronic properties considerably. The bonding character for adsorption outside the nanotube is mainly covalent, but inside it consists of physical bonding. The adsorption of several Cl atoms inside a carbon nanotube leads to the formation of a charged Cl chain. Our calculated desorption barrier of <= 1.4 eV per Cl atom pair indicates that the cleansing by chlorination is a less damaging alternative with removable residue.