LAUSR

Development of bifunctional electrocatalysts for oxygen electrocatalytic reactions is significant in improving the performance of Zn‐air batteries. Among all candidates, transition metal compounds and carbon nanotube composites have attracted considerable attention owing to their great catalytic activities. Herein, three‐dimensional (3D) macroporous carbon nanotube (CNT) microspheres interconnected with thorn‐like N‐doped CNT surrounding Co/CoO (m‐C@Co/CoO‐bC) are synthesized via spray pyrolysis, followed by N‐doped CNT growth and oxidation. Hierarchical nanohybrids with porous N‐doped CNT‐network and Co/CoO catalysts are rationally designed and applied as an efficient oxygen electrocatalyst. The porous carbon backbone exhibits high electrical conductivity with robust corrosion resistance. In addition, interconnected N‐doped CNTs wrapping Co/CoO nanocatalysts exhibit enhanced catalytic properties as compared to commercial Pt/C and RuO2 in alkaline media. m‐C@Co/CoO‐bC exhibits a robust cycle stability, higher power density, and lower polarization potential difference when applied as the oxygen electrode in a rechargeable Zn‐air battery, in comparison to commercial Pt/C‐RuO2 mixed powders.