Construction of pyrrolo[3,2-b]pyrrolyl-linked covalent organic polymers to promote continuous overall H2O2 production

Sacrificial agent-free, solar-driven photocatalytic oxygen reduction holds promise for hydrogen peroxide production. However, the rapid recombination of electron–hole pairs in catalysts and the slow diffusion rate of oxygen on the catalyst surfaces significantly hinder the efficiency of hydrogen peroxide production. To address these issues, we developed a novel class of pyrrolo[3,2-b]pyrrolyl-linked covalent organic polymers (COPs) combined with microreactor technology to enhance hydrogen peroxide synthesis. These structurally well-defined polymers feature photoactive pyrrolo[3,2-b]pyrrolyl units were assembled from aldehyde, aniline, and 2,3-butanedione through a one-pot three-component reaction. Integrating pyrrolo[3,2-b]pyrrolyl moieties into the COPs creates donor–acceptor structures that facilitate the separation of photogenerated electrons and holes. Among them, COP-2 achieved the highest H₂O₂ yield of 5446 μmol g⁻¹ h⁻¹. Furthermore, we designed a coiled tube photomicroreactor to improve mass transfer efficiency in the gas–liquid–solid triphase system, boosting the H₂O₂ yield to 20285 μmol g⁻¹h⁻¹ without the need for a sacrificial agent. This study offers new insights into integrating polymer photocatalysts with microflow technology, underscoring the potential for future green and continuous H₂O₂ production.