| Summary: | Exploiting cost-effective and durable non-platinum electrocatalysts for oxygen reduction reaction (ORR) is of great significance for the development of abundant renewable energy conversion and storage technologies. Herein, a series of Co<sub>3</sub>O<sub>4</sub> supported on graphene-like carbon (Co<sub>3</sub>O<sub>4</sub>/C) samples were firstly effectively synthesized by one-step calcination of cobalt phthalocyanine and their electrocatalytic performances were measured for ORR under an alkaline medium. By systematically adjusting the calcination temperature of cobalt phthalocyanine, we found that the material pyrolyzed at 750 °C (Co<sub>3</sub>O<sub>4</sub>/C−750) shows the best ORR electrocatalytic performance (half-wave potentials of 0.77 V (vs. RHE) in 0.1 M KOH) among all the control samples. Moreover, it displays better stability and superior methanol tolerance than commercial 20% Pt/C. The further electrochemical test results reveal that the process is close in characteristics to the four-electron ORR process on Co<sub>3</sub>O<sub>4</sub>/C−750. In addition, Co<sub>3</sub>O<sub>4</sub>/C−750 applied in the zinc–air battery presents 1.34 V of open circuit potential. Based on all the characterizations, the enhanced electrocatalytic performances of Co<sub>3</sub>O<sub>4</sub>/C−750 composite should be ascribed to the synergistic effect between Co<sub>3</sub>O<sub>4</sub> and the graphene-like carbon layer structure produced by pyrolysis of cobalt phthalocyanine, as well as its high specific surface area.
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