Efficient Photocatalytic H ₂ O ₂ Production Based on Thiazaheterocyclic Functional Groups Linkages in Porous Organic Polymers

Porous organic polymers (POPs) have been widely explored as photocatalysts for artificial photosynthesis of hydrogen peroxide (H 2 O 2 ). However, current POP design strategies face limitations in charge‐separation efficiency and active site optimization. This study addresses these challenges by developing triptycene‐linked donor–acceptor (D–A) POPs functionalized with benzobisthiazole (BBT) and benzothiadiazole (BT) units, which are thiazaheterocyclic functional groups exhibiting distinct conjugation degrees and heteroatom densities. Multidimensional investigations reveal how these structural parameters regulate charge transfer dynamics and oxygen activation capabilities. Both POPs exhibit well‐defined porosity and efficient charge separation. Especially BBT‐POPs, featuring higher conjugation and heteroatom content, demonstrate superior oxygen activation in pure water with H 2 O 2 production rate of 6775 μmol·g −1 after 2 h of light irradiation, which is threefold higher than BT‐POPs (2280 μmol·g −1 ), and the generated H 2 O 2 enables efficient dye degradation, confirming practical utility. Mechanistic studies attribute BBT‐POPs' enhanced performance to extended conjugation in D–A architectures, and N/S‐heteroatom sites provide abundant heteroatom sites, which collectively promote charge separation and reactive oxygen species interaction. This work elucidates the critical role of heteroatom functionalization in photocatalyst design, providing important insights for optimizing POPs architectures toward efficient solar‐driven H 2 O 2 production.