Synergistic Strategy toward Enhancing Photosynthesizing Reactive Oxygen Species of Covalent Organic Frameworks

Abstract Photocatalytic reactive oxygen species (ROSs) plays an important role in photodynamic therapy and photochemical reactions. However, most reported photocatalysts suffer from insufficient utilization of visible light and low conversion of O₂, which requires the development of higher performance catalysts toward practical applications. Herein, a series of porphyrin‐based COFs have been prepared. Comparative experimental and theoretical studies have revealed that the synergistic interaction between the two building blocks can significantly enhance the yields of ROSs by independently accomplishing photon harvesting and oxygen capture with smooth energy transfer between them. Particularly, the ¹O₂ yield of 3P‐Por‐COF is increased to 1.3 and 3.4 times that of the classical PCN‐224 and porphyrin molecular aggregates. Furthermore, the TOF of 3P‐Por‐COF is as high as 271 h⁻¹ with ≈100% selectivity under red light irradiation in catalyzing thioanisole to methyl phenyl sulfoxide. The conversion and stability of degradation of toluene gas under natural light are also superior to the conventional Fenton catalytic system. The present results should contribute to the design of high‐performance frameworks‐based photocatalysts for ROSs production.