Boosting Graphene Reactivity with Oxygen by Boron Doping: Density Functional Theory Modeling of the Reaction Path.

Graphene (G) reactivity toward oxygen is very poor, which limits its use as electrode for the oxygen reduction reaction (ORR). Contrarily, boron-doped graphene was found to be an excellent catalyst for the ORR Through a density functional study, comparing molecular and periodic approaches and different functionals (B3LYP vs PBE), we show how substitutional boron in the carbon sheet can boost the reactivity with oxygen leading to the formation of bulk borates covalently bound to graphene (BO3-G) in oxygen-rich conditions. These species are highly interesting intermediates for the O=O breaking step in the reduction process of O-2 to form H2O as they are energetically stable.