Regulating the generation of reactive oxygen species for photocatalytic oxidation by metalloporphyrinic covalent organic frameworks

[Display omitted] •Three new hydrazone-linked two-dimensional porphyrinic COFs were constructed.•The generation of 1O2 and O2•− species is selectively controlled by the COF structure.•Copper porphyrin-based COF shows the best activity in 1O2-involved oxidation.•COF-incorporated cobalt porphyrin exhibited the highest activity in O2•−-mediated oxidation.•The 1O2 and O2•− generation is correlated to band structure and O2 adsorption ability of the COFs. Regulating the generation of reactive oxygen species (ROS) impacts the selectivity and activity of photocatalytic oxidation, but the frequently concurrent formation of different types of ROS makes this process rather challenging. This study demonstrates the regulated production of two important ROS, 1O2 and O2•−, using a covalent-organic framework (COF) array with three members, which are made up of metalloporphyrin cores with embedded center metal ions from d-block transition metals sequentially arranged in the periodic table. Due to the evolution of the electronic structures in this COF array, the production of 1O2 and O2•− is controlled, which successively leads to distinct performance in photocatalytic aerobic oxidations. The electronic property study and density-functional theory (DFT) calculations revealed that the distinct excitonic behavior of three COFs in regulated 1O2 and O2•− generation is rooted in their different band energy levels and O2 adsorption ability. Our work presents an effective approach to the controlled production of ROS for improved photocatalytic performance.