Fluorination of multiwall nitrogen-doped carbon nanotubes

A film of oriented nitrogen-doped multiwall carbon nanotubes was grown on a silicon substrate as a result of the thermolysis of an acetonitrile + ferrocene mixture. The fluorination of the film by BrF3 vapor at room temperature removed the substrate; however, the vertical orientation of the nanotubes was not destroyed. Analysis of micrographs of a fluorinated sample obtained with a high-resolution transmission electron micro-scope showed that only the surface walls of the nanotubes were fluorinated. The fluorine concentration of the product as determined from X-ray photoelectron spectroscopy was about 16%. A comparison of the N1s spectra of the starting and fluorinated samples showed that the nitrogen atoms of CNx nanotubes changed their electronic state as a result of fluorination. Matching of the X-ray photoelectron spectroscopic data with the results of quantum-chemical calculations for fragments of fluorinated nitrogen-doped nanotubes showed that fluorine atoms preferred to attach to pyridine-like nitrogen atoms or to carbon atoms in the ortho or meta positions relative to a nitrogen atom.