Intelligent Hierarchical Micro–Mesoporous Nanoarchitectures: Engineering Pore Connectivity and Active-Site Cooperativity for Multifunctional Catalytic Systems

:Hierarchical porous catalysts now benefit from intentional co-design of transport pathways and catalytic functionality. This review critically examines intelligent micro–mesoporous nanoarchitectures, emphasizing pore connectivity and active-site cooperativity as inseparable design principles. We first outline limitations of purely microporous systems (diffusion constraints, site inaccessibility, deactivation) and then show how multi-scale networks overcome these issues. Engineering strategies for pore connectivity involving bottom-up templating, post-synthetic reconstruction, top-down desilication/dealumination are systematically reviewed alongside metrics (tortuosity, connectivity, accessibility). Active-site cooperativity is examined via acid-based bifunctionality, metal-acid coupling, single-atom catalysis and compartmentalized architectures for cascade reactions. The central thesis is that optimal performance emerges when transport and catalytic site engineering are coupled, supported by evidence from zeolites, metal–organic frameworks, silica nanoreactors, heteroatom-doped carbons and advanced electrocatalysts. Applications include biomass upgrading, selective oxidation, and energy conversion. The review also covers stability, deactivation, and regeneration, suggests standardized reporting criteria, and highlights future challenges such as using AI for catalyst design, operando transport mapping, scalable catalyst synthesis, and programmable catalytic nanoarchitectures. This review offers a predictive design strategy for next-generation multifunctional catalytic materials by focusing on the integrated transport-reaction system instead of only focusing on the structure.