Metal–Organic Framework-Derived Electrocatalysts for Rechargeable Zinc–Air Batteries

Rechargeable zinc–air batteries (ZABs) are still impeded by the intrinsically sluggish kinetics of oxygen reduction and evolution reactions (ORR/OER) and by the instability or prohibitive price of state-of-the-art noble metal catalysts. Metal–organic frameworks (MOFs) have recently emerged as versatile sacrificial templates for next-generation air–cathode electrocatalysts. By programming pyrolytic or chemical conversion pathways, MOFs can be quantitatively transformed into hierarchically porous, heteroatom-doped carbon scaffolds that embed uniform metal, alloy, or metal-oxide nanodomains. The resulting architectures couple metallic conductivity with molecular-scale active site tunability, delivering exceptional ORR/OER activity, stability, and mass transport properties. This review critically examines the most recent advances in MOF-derived electrocatalysts for ZABs, establishing quantitative structure–composition–performance relationships across mono-, bi-, and multi-metallic systems. Emphasis is placed on deciphering how framework topology, metal–ligand coordination, and post-synthetic parameters dictate the density, electronic structure, and accessibility of surface-active moieties during catalyst evolution. We further dissect engineering strategies that enhance intrinsic activity via electronic modulation, bolster durability through encapsulation effects, and optimize hierarchical porosity for rapid O2/water transport. This article concludes by outlining unresolved challenges and future research directions, including atomically precise active site construction, multi-scale compositional control, long-term reversibility under realistic ZABs cycles, scalable and green synthesis, providing a roadmap for translating MOF-derived catalysts from laboratory curiosities to commercially viable air–cathode materials.