Real-time mechanistic study of carbon nanotube anion functionalisation through open circuit voltammetry.

ABSTRACT: The mechanism of the functionalisation of reduced single walled carbon nanotubes with organobromides was monitored by open circuit voltammetry throughout the reaction and further elucidated through a series of comparative reactions. The degree of functionalisation was mapped against the reagent reduction potential, degree of electron donation of substituents (Hammett parameter), and energies calculated, ab initio, for dissociation and heterolytic cleavage of the C-Br bond. In contrast to the previously assumed reduction/homolytic cleavage mechanism, the reaction was shown to consist of a rapid association of carbon-halide bond to the reduced nanotube as a complex, displacing surface-condensed countercations, leading to an initial increase in the net nanotube surface negative charge.

SUBMITTER: Clancy AJ 

PROVIDER: S-EPMC6428032 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature