Truncated Conjugate Structure Improves Solar‐Driven Hydrogen Peroxide Production Catalyzed by Benzobisthiazole‐Based Conjugated Polymers

In this work, a novel molecular design strategy was employed to truncate large‐scale conjugated structures in covalent polymer materials. This approach significantly enhances the catalyst’s light‐harvesting capability, prolongs the lifetime of photogenerated charge carriers, and improves catalytic activity, thereby offering a new conceptual pathway for designing highly efficient photocatalysts. Abstract The solar‐driven production of hydrogen peroxide from water and air presents a promising and sustainable alternative to the conventional anthraquinone oxidation process. In this work, a series of benzobisthiazole‐based conjugated polymers with tailored 1D, 2D, and 3D architectures are successfully constructed through precise dimensional engineering and molecular structure design. The study demonstrates that the 3D benzobisthiazole‐based conjugated polymer material (BBTz‐3D) possesses unique advantages due to its discontinuous conjugated structure. It can effectively utilize the truncation effect of sp3 C atoms in its molecular framework, which leads to the formation of localized electronic states within the material, thereby hindering the electron transfer pathway. Furthermore, the introduction of benzobisthiazole units expands the light absorption range of the system and facilitates the charge separation of photogenerated carriers. Therefore, the optimized system achieves a hydrogen peroxide generation rate of 7970.51 µmol g−1 h−1 in pure water. Moreover, under natural sunlight irradiation for three hours, the photocatalytic system demonstrated exceptional performance in Erhai Lake water, achieving a substantial hydrogen peroxide production of 6737.27 µmol g−1. This research presents a valuable approach for the rational design and synthesis of high‐performance organic photocatalysts, offering significant advancements in both fundamental understanding and practical applications of solar energy conversion. In this work, a novel molecular design strategy was employed to truncate large-scale conjugated structures in covalent polymer materials. This approach significantly enhances the catalyst’s light-harvesting capability, prolongs the lifetime of photogenerated charge carriers, and improves catalytic activity, thereby offering a new conceptual pathway for designing highly efficient photocatalysts. Abstract The solar-driven production of hydrogen peroxide from water and air presents a promising and sustainable alternative to the conventional anthraquinone oxidation process. In this work, a series of benzobisthiazole-based conjugated polymers with tailored 1D, 2D, and 3D architectures are successfully constructed through precise dimensional engineering and molecular structure design. The study demonstrates that the 3D benzobisthiazole-based conjugated polymer material (BBTz-3D) possesses unique advantages due to its discontinuous conjugated structure. It can effectively utilize the truncation effect of sp 3 C atoms in its molecular framework, which leads to the formation of localized electronic states within the material, thereby hindering the electron transfer pathway. Furthermore, the introduction of benzobisthiazole units expands the light absorption range of the system and facilitates the charge separation of photogenerated carriers. Therefore, the optimized system achieves a hydrogen peroxide generation rate of 7970.51 µmol g −1 h −1 in pure water. Moreover, under natural sunlight irradiation for three hours, the photocatalytic system demonstrated exceptional performance in Erhai Lake water, achieving a substantial hydrogen peroxide production of 6737.27 µmol g −1. This research presents a valuable approach for the rational design and synthesis of high-performance organic photocatalysts, offering significant advancements in both fundamental understanding and practical applications of solar energy conversion. Advanced Science, EarlyView.