A defect-rich interconnected hierarchical three-dimensional Fe and N co-doped graphene has been prepared by a facile synthesis with poly (2,5-benzimidazole) (ABPBI) as nitrogen and carbon sources and CaCO as the template. ABPBI possesses abundant nitrogen, and pyrolysis of ABPBI is helpful to form graphene structure. CaCO and its decomposition products CO can promote the formation of interconnected hierarchical porous three-dimensional graphene, which possesses more defects and exposed active sites. Benefiting from the defective catalysis mechanism, rich defect catalysts are applied as electrode materials to enhance the catalytic performance for oxygen reduction reaction (ORR). Electrochemically, the half-wave potential (E ) of Fe-3D-NG#800 is 0.84 V (vs. RHE), and the accelerated durability tests shows the E of Fe-3D-NG#800 shifted by a 21 mV drop after cyclic voltammetry scanning for 5000 cycles. Therefore, Fe-3D-NG#800 has excellent activity and durability than 20 wt % Pt/C.
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