Pyrene‐Based Covalent Organic Frameworks for Photocatalytic Hydrogen Peroxide Production

Abstract Four highly porous covalent organic frameworks (COFs) containing pyrene units were prepared and explored for photocatalytic H 2 O 2 production. The experimental studies are complemented by density functional theory calculations, proving that the pyrene unit is more active for H 2 O 2 production than the bipyridine and (diarylamino)benzene units reported previously. H 2 O 2 decomposition experiments verified that the distribution of pyrene units over a large surface area of COFs plays an important role in catalytic performance. The Py‐Py‐COF though contains more pyrene units than other COFs which induces a high H 2 O 2 decomposition due to a dense concentration of pyrene in close proximity over a limited surface area. Therefore, a two‐phase reaction system (water‐benzyl alcohol) was employed to inhibit H 2 O 2 decomposition. This is the first report on applying pyrene‐based COFs in a two‐phase system for photocatalytic H 2 O 2 generation.