Active Sites and Mechanism of Oxygen Reduction Reaction Electrocatalysis on Nitrogen-Doped Carbon Materials.

The oxygen reduction reaction (ORR) is a core reaction for electrochemical energy technologies such as fuel cells and metal-air batteries. ORR catalysts have been limited to platinum, which meets the requirements of high activity and durability. Over the last few decades, a variety of materials have been tested as non-Pt catalysts, from metal-organic complex molecules to metal-free catalysts. In particular, nitrogen-doped graphitic carbon materials, including N-doped graphene and N-doped carbon nanotubes, have been extensively studied. However, due to the lack of understanding of the reaction mechanism and conflicting knowledge of the catalytic active sites, carbon-based catalysts are still under the development stage of achieving a performance similar to Pt-based catalysts. In addition to the catalytic viewpoint, designing mass transport pathways is required for O2 . Recently, the importance of pyridinic N for the creation of active sites for ORR and the requirement of hydrophobicity near the active sites have been reported. Based on the increased knowledge in controlling ORR performances, bottom-up preparation of N-doped carbon catalysts, using N-containing conjugative molecules as the assemblies of the catalysts, is promising. Here, the recent understanding of the active sites and the mechanism of ORRs on N-doped carbon catalysts are reviewed.