Metal-free doped carbon materials as electrocatalysts for the oxygen reduction reaction

Carbon materials such as graphite, graphene, carbon nanotubes and ordered mesoporous carbon have attracted a lot of attention for their use in fuel cells, due to beneficial properties like high conductivity, high mechanical and chemical stability and, for the latter, high surface area. Doping these materials with nitrogen or, less commonly, other elements alters their (electronic) properties, making them particularly suitable for application as electrocatalysts for the oxygen reduction reaction (ORR) in a fuel cell. This paper reviews the synthesis methods employed for the doping of these different types of carbon materials with various elements and the characterization techniques used to investigate their physicochemical properties such as degree of graphitization, dopant content, dopant configuration and surface area. Furthermore, their application as electrocatalysts for the oxygen reduction in a fuel cell is reviewed. Finally, the possible mechanisms for the ORR on N-doped carbon materials are critically discussed and compared to the mechanisms of commercial Pt/C electrocatalysts.