Carbon Nanotubes Assembled Ordered Macro‐Microporous Superstructure as Bifunctional Oxygen Electrocatalyst for Long‐Life Rechargeable Zn–Air Batteries

ABSTRACT Achieving precise fabrication of ordered superstructures with multifunctional catalytic activity is fascinating but elusive due to uncontrollable interfacial energy and growth kinetics at the material surface. Herein, we develop a facile strategy for oriented formation of carbon nanotubes (CNT) anchored on three‐dimensionally ordered macro‐microporous (3DOM) superstructure derived from a Co‐based 3DOM metal‐organic framework (3DOM‐MOF). Mechanism studies based on density functional theory (DFT) calculations and in situ spectroscopy reveal that the synergistic coupling of curved CNTs supports and Co nanoparticles in the as‐prepared Co‐based porous superstructures CNTs catalysts (Co‐HOPS‐CNTs _20D ) can regulate the electronic structure of the isolated Co‐N ₄ sites, thus optimizing the binding strength of the oxygenated intermediates and facilitating intrinsic catalyst activity. The unique feature of the superstructure is validated using 3D transmission electron microscopy tomography, and the corresponding finite element analysis (FEA) simulations prove enhanced conductivity of Co‐HOPS‐CNTs _20D superstructure, which facilitates transfer efficiency of electrons and improves catalytic activity. As a result, the Co‐HOPS‐CNTs _20D exhibits a low overpotential of 287 mV at 10 mA cm ⁻² for OER and a high ORR half‐wave potential of 0.863 V. The zinc‐air battery incorporating Co‐HOPS‐CNTs _20D demonstrates efficient and stable operation over a period of 160 h.