Non-noble-metal-based electrocatalysts with superior oxygen reduction reaction (ORR) activity to platinum (Pt) are highly desirable but their fabrications are challenging and thus impeding their applications in metal-air batteries and fuel cells. Here, we report a facile molten salt assisted two-step pyrolysis strategy to construct carbon nanosheets matrix with uniformly dispersed Fe3N/Fe nanoparticles and abundant nitrogen-coordinated Fe single atom moieties (Fe@FeSA-N-C). Thermal exfoliation and etching effect of molten salt contribute to the formation of carbon nanosheets with high porosity, large surface area and abundant uniformly immobilized active sites. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) image, X-ray absorption fine spectroscopy, and X-ray photoelectron spectroscopy indicate the generation of Fe (mainly Fe3N/Fe) and FeSA-N-C moieties, which account for the catalytic activity for ORR. Further study on modulating the crystal structure and composition of Fe3N/Fe nanoparticles reveals that proper chemical environment of Fe in Fe3N/Fe notably optimizes the ORR activity. Consequently, the presence of abundant FeSA-N-C moieties, and potential synergies of Fe3N/Fe nanoparticles and carbon shells, markedly promote the reaction kinetics. The as-developed Fe@FeSA-N-C-900 electrocatalyst displays superior ORR performance with a half-wave potential (E1/2) of 0.83 V versus reversible hydrogen electrode (RHE) and a diffusion limited current density of 5.6 mA cm2. In addition, a rechargeable Zn-air battery device assembled by the Fe@FeSA-N-C-900 possesses remarkably stable performance with a small voltage gap without obvious voltage loss after 500 h of operation. The facile synthesis strategy for the high-performance composites represents another viable avenue to stable and low-cost electrocatalysts for ORR catalysis.
