Enhanced Photocatalytic Activity of Hyper‐Cross‐Linked Polymers Toward Amines Oxidation Coupled with H2O2 Generation through Extending Monomer's Conjugation Degree

Abstract Visible‐light‐driven amines oxidation coupled with hydrogen peroxide (H 2 O 2 ) generation is a promising way to convert solar energy to chemical energy. Herein, a series of hyper‐cross‐linked polymers (HCPs) photocatalysts with different arenes monomers, including benzene (BE), diphenyl (DP), p‐terphenyl (TP), or p‐quaterphenyl (QP), were synthesized by simple Friedel–Crafts alkylation reaction. Owing to the maximum monomer's conjunction degree and excellent oxygen (O 2 ) adsorption capacity, QP‐HCPs exhibited highest photocatalytic activity for benzylamine oxidation coupled with H 2 O 2 generation under the irradiation of 455 nm Blue LED lamp. More than 99 % of benzylamine could be converted to N‐benzylidenebenzylamine within 60 min. In addition, nearly stoichiometric H 2 O 2 was synchronously obtained with a high production rate of 9.3 mmol g cat −1 h −1 . Our work not only demonstrated that the photocatalytic activity of HCPs photocatalysts significantly depends on monomer's conjunction degree, but also provided a new strategy for converting solar energy to chemical energy.