Dynamic Reconstruction of Metal–Organic Framework and Metal–Organic Framework‐Derived Electrocatalysts for Bifunctional Oxygen Electrocatalysis in Alkaline Energy Devices

ABSTRACT

Alkaline oxygen reduction reaction (ORR)/OER bifunctionality is central to rechargeable Zn–air batteries, reversible fuel cells and regenerative electrolysis. These technologies are promising for mitigating carbon emissions resulting from fossil fuel energy dependency, driving the energy sector towards a carbon‐neutral energy cycle. Due to their excellent intrinsic activity, metal–organic frameworks (MOFs) and their derivatives have emerged as promising materials for bifunctional oxygen electrocatalysis. Despite their great activity, MOFs often transform under operating potential. The key unresolved issue is identifying the true active phase and linking precursor structure to reconstructed active sites. This review highlights the use of MOF‐based electrocatalysts, their reconstruction and stability during bifunctional electrocatalysis for ORR and OER in alkaline medium. Pristine MOFs, conductive MOFs, MOF composites and MOF‐derived carbons/oxides/phosphides/sulphides are critically compared. It further proposes design rules based on conductivity, metal‐node chemistry, ligand‐derived heteroatom doping, porosity, active‐site reconstruction and device‐level validation. A comprehensive summary of the progress in MOF‐based and MOF‐derived electrocatalysts for ORR and OER, from design to future perspectives, is presented, with possible solution strategies for future design and preparation.