Pore-zoned nanoarchitectonics of hierarchically porous metal–organic frameworks (MOFs) and MOF-derived materials for electrochemical energy conversion

Hierarchically porous metal-organic frameworks have emerged as a versatile platform for overcoming the mass transfer limitations of conventional microporous materials. However, the true potential of these materials lies not merely in increasing pore volume, but in the functional integration of distinct pore domains. Herein, we articulate the concept of pore-zoned nanoarchitectonics, a rational design paradigm that orchestrates reactants across varying length scales. We elucidate how this architecture creates a synergistic environment: micropores serve as confined redox centers for thermodynamic stabilization, mesopores act as kinetic buffers for intermediate management, and macropores function as high-flux reservoirs for phase boundary regulation. This review comprehensively summarizes state-of-the-art synthetic strategies—ranging from ligand engineering and defect formation to hard/soft templating and composite-derived approaches—that enable such precise structural programming. Furthermore, we highlight the transformative impact of these architectures in electrocatalysis, demonstrating how pore-zoned engineering resolves the intrinsic trade-off between mass transport velocity and active site density. Finally, we provide a roadmap for the future, emphasizing the transition from static porous solids to intelligent, adaptive energy conversion systems.