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Transition metal- and N-codoped carbon catalysts with low cost are latent substitutes to Pt-based catalysts in oxygen reduction reaction. However, the variety of N species obtained by pyrolysis often makes the determination of the active site controversial. Here, we design catalyst structures with pyrrolic-N anchored dual metal centers, while the presence of pyrrolic-N avoids the complex and variable structure of the active sites. Theory calculations demonstrate that coupling of the Cu–N 4 single-atom sites is favorable to reduce the reaction energy barrier of pyrrolic-N-type Fe–N 4 active site during the reaction process. Subsequently, the high-purity pyrrolic-N-type iron and copper single-atom catalyst is successfully synthesized to verify the hypothesis. The obtained FeCu–N–C catalyst achieves a half-wave potential of 0.913 V, higher than the 0.839 V of Pt/C. This route may provide new insights for regulating catalytic active sites in high purity pyrrolic-N type catalysts. The introduction of Cu single-atom optimizes the pyrrolic-N-type Fe–N 4 active site of the FeCu–N–C, endowing the catalyst with remarkable ORR activity (E 1/2 = 0.913 V). [Display omitted] • A pyrrolic-N anchors dual metal centers structure is designed. • DFT calculations demonstrate Cu doping can improve the ORR activity of iron sites. • Catalysts with high purity pyrrolic-N are prepared to prove the DFT calculations. • The half-wave potential of the obtained FeCu–N catalyst reaches 0.913 V. • This strategy provides new insights for regulating active sites of ORR. [ABSTRACT FROM AUTHOR]

Sluggish oxygen reduction reaction (ORR) kinetics is the biggest obstacle in the development of metal air batteries. High-efficiency ORR catalysts with low cost are in urgent needs. Herein, we propose a robust Fe–N–C ORR catalyst with highly dispersed Fe-N x active sites on graphitic-N dominated porous carbon. The synchrotron radiation analyses reveal the discrete Fe-N x coordination derived from the Prussian blue (PB) while the graphitic-N doped porous carbon formed by pyrolysis of the polyaniline (PANI). In virtue of their synergistic catalysis, the tailored Fe–N–C catalyst shows a comparable catalytic activity and a better methanol-tolerance than the commercial Pt/C catalyst. The assembled Zn-Air battery demonstrates a specific capacity of 783 mAh g−1 as well as energy density of 917 Wh kg−1 at 10 mA cm−2, and a maximum power density of 112 mW cm−2 at 191 mA cm−2. A robust Fe– N –C ORR catalyst derived from PB-anchored PANI with well-dispersed Fe-N x active sites on graphitic-N dominated porous carbon host shows comparable performance to the commercial Pt/C catalyst. Image 1 [ABSTRACT FROM AUTHOR]