A "MOF-Protective-Pyrolysis" Strategy for the Preparation of Fe-N-C Catalysts and the Role of Fe, N, and C in the Oxygen Reduction Reaction in Acidic Medium.

M-N-C electrocatalysts for the oxygen reduction reaction (ORR) have been considered as the most promising alternatives to precious metal catalysts. However, the catalytic activity of M-N-C especially in an acidic medium is still unable to meet the practical requirement, and the corresponding ORR mechanism also remains unclear. Herein, an "MOF-protective-pyrolysis" strategy was adopted to synthesize an Fe-N-C catalyst (P-FeMOF@ZIF-8) with Fe-N4 as the predominant Fe species. The P-FeMOF@ZIF-8 displays high catalytic activity in both acidic and alkaline mediums. The experimental results further reveal the different importance of the Fe species in different mediums. Based on the results, a distinct mechanism of the ORR the in acidic medium was proposed, where the synergistic effect of the Fe-N4 site and carbon in improving the kinetics of the ORR were well explained. The findings and the corresponding perspective may provide a new guidance for the design of highly efficient ORR electrocatalysts.