Recent Advances in Porphyrin-Based COFs Boosting CO₂ Photocatalytic and Electrocatalytic Conversion

Porphyrins are conjugated tetrapyrrolic macrocycles with tunable photophysical and catalytic properties, while covalent organic frameworks (COFs) are crystalline, porous polymers built from robust covalent linkages. Combining these motifs yields porphyrin-based COFs that couple ordered porosity with light-harvesting and metal-anchoring capabilities, offering promise for carbon dioxide capture and conversion. This review provides an integrated overview of their design, synthesis, structure, and function in the context of CO₂ capture, storage, and photocatalytic/electrocatalytic reduction. We survey recent literature, organize materials by linkage chemistry and topology, and summarize metallation, peripheral functionalization, and heterostructure strategies, compiling representative performance metrics where reported. The collected studies indicate that appropriate metallation and π-extension enhance light absorption and charge separation; high crystallinity and accessible pores facilitate mass transport; and electronic coupling to conductive phases improves catalytic activity and selectivity in CO₂ reduction. We close by outlining challenges and opportunities, including improving charge transport without sacrificing stability, pinpointing and quantifying active sites, and operando characterization to connect structure with function. This objective synthesis is intended to guide rational design of porphyrin-COFs for efficient and durable CO₂ management.