▎ 摘　　要

Chemical doping with foreign atoms is an effective method to intrinsically modify the electronic properties of graphene. Besides, the hydration with metal oxide particles toward oxygen reduction with high activity can further improve its electrocatalysis performance. Furthermore, a hierarchical structure can provide sufficient pathways to certify the diffusion of electrolyte and electron transfer. In this paper, we developed a novel three-dimensional nitrogen-doped reduced graphene oxide/manganese monoxide composite (3D-N-RGO/MnO) by incorporating covalent assembly and nitrogen doping. The as-prepared 3D-N-RGO/MnO was further applied for oxygen reduction reaction (ORR). By the synergistic effect of three-dimensional nitrogen-doped graphene (3D-N-RGO) and MnO, catalytic performance brings enhanced catalytic current and more positive potential. In addition, 3D-N-RGO/MnO exhibits excellent methanol tolerance and long-term stability.