Fracturing graphene by chlorination: a theoretical viewpoint

Physics – Condensed Matter – Mesoscale and Nanoscale Physics

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Scientific paper

Motivated by the recent photochlorination experiment [B. Li et al., ACS Nano 5, 5957 (2011)], we study theoretically the interaction of chlorine with graphene. In previous theoretical studies, covalent binding between chlorine and carbon atoms has been elusive upon adsorption to the graphene basal plane. Interestingly, in their recent experiment, Li et al. interpreted their data in terms of chemical bonding of chlorine on top of the graphene plane, associated with a change from sp2 to sp3 in carbon hybridization and formation of graphene nanodomains. We study the hypothesis that these domains are actually fractured graphene with chlorinated edges, and compare the energetics of chlorine-containing graphene edge terminations, both in zigzag and armchair directions, to chlorine adsorption onto infinite graphene. Our results indicate that edge chlorination is favored over adsorption in the experimental conditions with radical atomic chlorine and that edge chlorination with sp3-hybridized edge carbons is stable also in ambient conditions. An ab initio thermodynamical analysis shows that the presence of chlorine is able to break the pristine graphene layer. Finally, we discuss the possible effects of the silicon dioxide substrate on the chlorination of graphene.

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