Topology-Engineered Three-Dimensional Porphyrin-Based Covalent Organic Frameworks for Photo- and Electrocatalysis

Photo- and electrocatalytic conversion of abundant resources into value-added chemicals is a promising route to address rising energy demands and environmental sustainability. Achieving high efficiency requires catalysts that promote rapid charge generation, separation, and transport. Porphyrin-based covalent organic frameworks (Por-COFs) provide well-defined modular architectures with tunable electronic structures. Although two-dimensional (2D) Por-COFs can offer fast in-plane charge transport via extended π-conjugation, their densely stacked layers often impede mass diffusion and limit interlayer charge migration. By contrast, three-dimensional (3D) Por-COFs feature interconnected open channels and fully exposed active sites, enabling efficient charge separation, multidirectional charge transport, and improved accessibility of reactants and guests. These attributes translate into enhanced photo- and electrocatalytic activity. This article summarizes recent progress in the design and catalytic applications of 3D Por-COFs, emphasizing topology-guided structural engineering, performance optimization strategies, and structure-property-activity relationships. Remaining challenges and future opportunities are discussed to guide mechanistic understanding and accelerate practical implementation.