Balance of N-Doping Engineering and Carbon Chemistry to Expose Edge Graphitic N Sites for Enhanced Oxygen Reduction Electrocatalysis.

ABSTRACT

Nitrogen-doped nanocarbon materials (NCMs) have been developed as promising metal-free oxygen reduction reaction (ORR) electrocatalysts. However, insufficient attention on the balance of N-doping engineering and carbon chemistry significantly suppressed the revelation of the real active configurations as well as the ORR mechanism for NCMs. Herein, 1,4-phenylenediurea (BDU) with multifunctional blocks was designed for the synthesis of NCMs, realizing synchronous manipulation of N-doping engineering and carbon chemistry. The good balance between N-doping engineering (especially graphitic edge N configurations) and carbon chemistry (including the specific surface area, porosity distribution, and graphitization degree) at a pyrolysis temperature of 1000 °C resulted in the best ORR performance for obtaining N-doped carbon nanorod (NCR) materials. A general descriptor χ was then proposed for evaluating the balance states between N-doping engineering and carbon chemistry. The prediction of the ORR performance of NCMs from their physical properties as well as searching for the optimal active configuration from the relationships between ORR performance and different configurations can be realized from such a practical descriptor, which can also be extended to other nanocarbon-based metal-free electrocatalytic reactions for deeply understanding their electrocatalytic mechanisms.