Preparation of F and N Co‐Doped Fe–N–C Catalyst and Evaluation of its Oxygen Reduction Performance

The problems of underdeveloped pores and high electrochemical impedance of oxygen reduction reaction (ORR) catalysts need to be urgently addressed. Heteroatoms F and N are doped on precursor Fe‐zeolitic imidazolate framework (ZIF)‐8 to increase the activity of Fe‐ZIF‐8‐derived porous carbon materials and a noble metal‐free high‐activity ORR catalyst F–N/FeNC with 3D interconnected porous structure and high conductivity is successfully prepared. Experiments show that the synergistic effect of CF ionic bonds, pyridinic‐N, pyrrolic‐N, graphitic‐N, FeN x sites, and CF semi‐ionic bonds in F–N/FeNC can improve the ORR activity of the F–N/FeNC. The developed F–N/FeNC is advantageous with excellent specific surface area, ultra‐high electrical conductivity, and extremely high ORR mass transfer efficiency. As such, the F–N/FeNC has a high onset potential of 0.95 V (vs RHE) and a half‐wave potential of 0.84 V (vs RHE), implying excellent ORR performance even better than commercially available Pt/C catalyst. In addition, the carefully prepared F–N/FeNC demonstrated higher long‐term durability and excellent resistance to methanol influence compared with commercially available Pt/C catalyst. The developed strategy provides new insights into heteroatom‐doped metal–organic frameworks as a precursor of ORR catalysts.