Direct and initiated halogenation of carbon nanomaterials at low temperatures

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Abstract
Cryochemical reactions of the direct and initiated (by photolysis and radiolysis) halogenation of carbon nanomaterials (C60 fullerene, nanotubes, and nanofibers) at 77–240 K were investigated by the ESR, IR spectroscopy, and elemental analysis techniques. A high reactivity of C60 in reactions with fluorine and chlorine with the formation of corresponding derivatives was shown. High concentrations of radical intermediates indicating the radical chain halogenation of C60 were detected (the kinetic chain length for the chlorination process reaches 104–106 units). The amount of chlorine attached to fullerene is ∼35% and practically does not depend on the initiation mode (UV or γ-irradiation at doses up to 350 kGy). The mechanism of the cryochemical halogenation of C60 is considered within the limits of the model of multicenter synchronous transitions in a molecular complex consisting of several reactant molecules including molecular fluorine or chlorine and ensuring a net exothermic effect. The amount of chlorine added to nanotubes and nanofibers did not exceed 2.5–8%, thereby indicating a low reactivity of these materials under cryogenic conditions.

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