Building synergistic multiple active sites in branch-leaf nanostructured carbon nanofiber derived from MOF/COF hybrid for flexible wearable Zn-air battery

Covalent organic frameworks (COFs) and metal–organic frameworks (MOFs) have attracted growing attention in electrochemical energy storage and conversion systems (e.g., Zn-air batteries, ZABs) owing to their structural tunability, ordered porosity and high specific surface area. In this work, for the first time, the three-dimensional (3D) highly open catalyst (CNFs/CoZn-MOF@COF) possessing hierarchical porous structure and high-density active sites of uniform cobalt (Co) nanoparticles and metal-Nx (M-Nx, M = Co and Zn) is demonstrated, which is fabricated using electrospinning technique in combination with MOF/COF hybridization strategy and direct pyrolysis. Benefiting from the well-designed branch-leaf nanostructures, plentiful and uniform active sites on the MOF/COF-derived carbon frameworks, as well as the synergistic effect of multiple active sites, CNFs/CoZn-MOF@COF catalyst achieves superior electrocatalytic activity and stability towards both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with a small potential gap (ΔE = 0.75 V). In situ Raman spectroscopy and X-ray photoelectron spectroscopy results indicate that the CoOOH intermediates are the main active species during OER/ORR. Significantly, both aqueous and all-solid-state rechargeable ZABs assembled with CNFs/CoZn-MOF@COF as the air cathode show high open-circuit potential, outstanding peak power density, large capacity and long cycle life. More impressively, the obtained all-solid-state ZAB also displays superb mechanical flexibility and device stability under different, showcasing great application deformations potential in portable and wearable electronics. This work provides a new insight into the design and exploitation of bifunctional catalysts from MOF/COF hybrid materials for energy storage and conversion devices.