In this study, we innovatively developed and optimized a novel double-layer structure of iron-nitrogen doped carbon-based SAC (FeSA-N5-C). FeSA-N5-C was screened as the best catalyst based on adsorption energy and reaction energy barriers among three catalysts (FeSA-N3-C, FeSA-N4-C and FeSA-N5-C). Secondly, the differences of three catalysts are revealed by the relationship between the d-band center and activation energy. In terms of experiments, we synthesized samples of iron-nitrogen-carbon (Fe-N-C) catalysts using pyrolysis of metal-organic framework materials. The coordination environment of Fe-N-C is also observed based on analyses including X-ray absorption near edge structure and extended X-ray absorption fine structure.