A Freestanding 3D Heterostructure Film Stitched by MOF‐Derived Carbon Nanotube Microsphere Superstructure and Reduced Graphene Oxide Sheets: A Superior Multifunctional Electrode for Overall Water Splitting and Zn–Air Batteries

Abstract Developing a scalable approach to construct efficient and multifunctional electrodes for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) is an urgent need for overall water splitting and zinc–air batteries. In this work, a freestanding 3D heterostructure film is synthesized from a Ni‐centered metal−organic framework (MOF)/graphene oxide. During the pyrolysis process, 1D carbon nanotubes formed from the MOF link with the 2D reduced graphene oxide sheets to stitch the 3D freestanding film. The results of the experiments and theoretical calculations show that the synergistic effect of the N‐doped carbon shell and Ni nanoparticles leads to an optimized film with excellent electrocatalytic activity. Low overpotentials of 95 and 260 mV are merely needed for HER and OER, respectively, to reach a current density of 10 mA cm −2 . In addition, a high half‐wave potential of 0.875 V is obtained for the ORR, which is comparable to that of Pt/RuO 2 and ranks among the top of non‐noble‐metal catalysts. The use of an “all‐in‐one” film as the electrode leads to excellent performance of the homemade water electrolyzer and zinc–air battery, indicating the potential of the film for practical applications.