Theoretical Studies of Oxygen Reactivity of Free-Standing and Supported Boron-Doped Graphene

Graphene inertness towards chemical reactivity can be considered as an accepted postulate by the research community. This limit has been recently overcome by chemically and physically modifying graphene through non-metal doping or interfacing with acceptor/donor materials (metals or semiconductors). As a result, outstanding performances as catalytic, electrocatalytic, and photocatalytic material have been observed. In this critical Review we report computational work performed, by our group, on the reactivity of free-standing, metal- and semiconductor-supported B-doped graphene towards oxygen, which is at the basis of extremely important energy-related chemical processes, such as the oxygen reduction reaction. It appears that a combination of doping and interfacing approaches for the activation of graphene can open unconventional and unprecedented reaction paths, thus boosting the potential of modified graphene in many chemical applications. Boron found to matter: Advanced density functional studies on the enhancement of oxygen reactivity through non-metal doping and/or interfacing graphene with metal (copper) and semiconductor (TiO2) surfaces are reviewed. Oxidized boron species are formed in the graphene sheets. These are bound to the underlying support through direct covalent bonds, which enhances the intimate connection between materials with different chemical and physical properties, thus creating an interactive hybrid interface.