Pre-fixing defects in carbon framework for revealing the active sites of oxygen reduction reaction at nitrogen-doped carbon nanotubes

Nitrogen-doped carbon-based materials are promising non-platinum group metal electrocatalysts for the oxygen reduction reaction (ORR). Understanding their ORR active sites is vital for the rational design and development of nitrogen-doped carbon-based electrocatalysts with enhanced catalytic efficiency and selectivity. However, the conclusive analysis of the ORR mechanism of nitrogen-doped carbon-based electrocatalysts remains a grand challenge because the catalysts have a complex inhomogeneous structure. Here, we elucidate this problem using nitrogen-doped carbon nanotubes framework catalysts with fixed defect concentrations prepared by pre-thermal treatment at a low temperature. The generation of defects under high-temperature treatment was effectively suppressed to enable a simple model for ORR mechanism study. A correlation between ORR pathways and the different nitrogen species in the nitrogen-doped carbon catalysts was revealed through a combination of structural and electrochemical properties investigations. Besides, our results also demonstrate the importance of defects for ORR. We believe that the results will provide instructive guidance for designing and developing novel carbon nanomaterials for ORR.