Graphene as Electrophile: Reactions of Graphene Fluoride

Fluorinated graphene obtained by exposing single-layer CVD-grown graphene to xenon difluoride was reacted with a series of amine-, alcohol-, and sulfur-bearing nucleophiles, and the progress and nature of the reactions were monitored using X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and conductivity measurements. The results of these experiments indicate that amine and alcohol nucleophiles can displace the fluorine groups to form covalent bonds to the graphene. For nucleophiles with more than one possible reactive site, close examination of XPS features reveals the orientation of these groups on the graphene. Sulfur nucleophiles act preferentially as reducing agents, removing fluorine rather than replacing it. Finally, a proof-of-principle nucleophilic substitution is performed on bulk graphite fluoride, showing that the chemical functionality of graphite can be extended through nucleophilic substitution in an analogous manner to that of single-layer graphene.