In situ solution plasma synthesis of nitrogen-doped carbon nanoparticles as metal-free electrocatalysts for the oxygen reduction reaction

We report the in situ synthesis of nitrogen-doped carbon nanoparticles (NCNPs) by a solution plasma process without the addition of metal catalysts. Organic liquid mixtures of benzene and pyrazine were used as the precursors for the synthesis. The nitrogen-doping content can be easily controlled by changing the amount of pyrazine in the precursor. The NCNPs synthesized from the solution plasma process exhibit a turbostratic structure with highly uniform nanoscale particles. The nitrogen atoms can be homogeneously incorporated into the entire carbon structure due to the in situ doping during the growth and formation of the carbon particles. The electrochemical activity toward the oxygen reduction reaction (ORR) of the NCNPs in an alkaline medium reveals the improvement in terms of both the onset potential and current density as the nitrogen-doping content increases. The enhanced ORR activity of the NCNPS is mainly attributed to the presence of pyridinic-N and graphitic-N bonding configurations. They also possess long-term durability and excellent tolerance to methanol crossover effects. The results obtained in this study have demonstrated that the solution plasma process has great potential for the synthesis of metal-free nitrogen-doped carbon electrocatalysts for the ORR. We expect that this approach can be extended to the synthesis of other heteroatom-doped carbonaceous materials for a broad range of research applications in energy conversion and storage.