MOF‐Mediated Fabrication of a Porous 3D Superstructure of Carbon Nanosheets Decorated with Ultrafine Cobalt Phosphide Nanoparticles for Efficient Electrocatalysis and Zinc–Air Batteries

Abstract Superstructures have attracted great interest owing to their potential applications. Herein, we report the first scalable preparation of a porous nickel‐foam‐templated superstructure of carbon nanosheets decorated with ultrafine cobalt phosphide nanoparticles. Uniform two‐dimensional (2D) Co‐metal organic framework (MOF) nanosheets (Co‐MNS) grow on nickel foam, followed by a MOF‐mediated tandem (carbonization/phosphidation) pyrolysis. The resulting superstructure has a porous 3D interconnected network with well‐arranged 2D carbon nanosheets on it, in which ultrafine cobalt phosphide nanoparticles are tightly immobilized. A single piece of this superstructure can be directly used as a self‐supported electrode for electrocatalysis without any binders. This “one‐piece” porous superstructure with excellent mass transport and electron transport properties, and catalytically active cobalt phosphide nanoparticles with ultrasmall size (3–4 nm), shows excellent trifunctional electrocatalytic activities for oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and oxygen reduction reaction (ORR), achieving great performances in water splitting and Zn–air batteries.