''Metal-free'' electrocatalysis: quaternary-doped graphene and the alkaline oxygen reduction reaction

We report the first investigation into a quaternary-doped graphene catalyst material for the oxygen reduction reaction (ORR) under alkaline conditions. The material was synthesized via direct pyrolysis of graphene oxide (GO) with boron, nitrogen, phosphorus and sulfur precursors. The resulting BNPSGr catalyst was thoroughly characterized and its composition found via XPS to be 6.4% (B), 6.1% (N), 2.6% (P) and 0.5% (S), while HR-TEM imaging shows a few-layered graphene structure. Electrochemical investigations into the catalytic activity towards the ORR show improved performance of the quaternary-doped graphene with the effective number of electrons transferred being ca. 3.7, compared to single-doped graphenes (2.9-3.2) and significantly lower peroxide production. This demonstrates BNPS-Gr to be a promising alternative to current Pt-group catalysts for the ORR, especially in methanol-fuelled fuel cells, where the presence of methanol in the cathode side from the fuel crossover is shown not to affect the performance of the quaternary-doped graphene catalyst.