Boosting Reactive Oxygen Species Generation by Regulating Excitonic Effects in Porphyrinic Covalent Organic Frameworks.

Excitonic effects play a crucial role in determining the photocatalytic performance of polymer semiconductors, which has long been ignored. Herein, metal organic frameworks (MOFs, specially NH 2 -MIL-125) modifying porphyrinic covalent organic frameworks (COFs, specially DhaTph) have been proven to be a suitable model to regulate excitonic effects. The photoluminescence measurements prove that DhaTph presents strong excitonic effects, which can generate 1 O 2 through an energy transfer process. Remarkably, the construction of the NH 2 -MIL-125@DhaTph heterostructure can effectively facilitate the dissociation of excitons, resulting in distinct activation of O 2 to O 2 •- and •OH. Benefiting from the enhanced generation of reactive oxygen species, the NH 2 -MIL-125@DhaTph composite exhibits a superior bactericidal effect and photocatalytic degradation performance. This work provides a deeper insight into the excitonic effects based on COFs during the photocatalytic process and opens a feasible avenue for the regulation of the excitonic effects in porphyrinic COFs.