Constructing Directional Electrostatic Potential Difference via Gradient Nitrogen Doping for Efficient Oxygen Reduction Reaction

Abstract Nitrogen doping has been recognized as an important strategy to enhance the oxygen reduction reaction (ORR) activity of carbon‐encapsulated transition metal catalysts (TM@C). However, previous reports on nitrogen doping have tended to result in a random distribution of nitrogen atoms, which leads to disordered electrostatic potential differences on the surface of carbon layers, limiting further control over the materials' electronic structure. Herein, a gradient nitrogen doping strategy to prepare nitrogen‐deficient graphene and nitrogen‐rich carbon nanotubes encapsulated cobalt nanoparticles catalysts (Co@CNTs@NG) is proposed. The unique gradient nitrogen doping leads to a gradual increase in the electrostatic potential of the carbon layer from the nitrogen‐rich region to the nitrogen‐deficient region, facilitating the directed electron transfer within these layers and ultimately optimizing the charge distribution of the material. Therefore, this strategy effectively regulates the density of state and work function of the material, further optimizing the adsorption of oxygen‐containing intermediates and enhancing ORR activity. Theoretical and experimental results show that under controlled gradient nitrogen doping, Co@CNTs@NG exhibits significantly ORR performance (E onset = 0.96 V, E 1/2 = 0.86 V). At the same time, Co@CNTs@NG also displays excellent performance as a cathode material for Zn–air batteries, with peak power density of 132.65 mA cm −2 and open‐circuit voltage (OCV) of 1.51 V. This work provides an effective gradient nitrogen doping strategy to optimize the ORR performance.