Amino Acid Modified Hyper‐Cross‐Linked Polymer Enabling High‐efficient Photocatalytic Amines Oxidation Coupled with H2O2 Production

Abstract The simultaneous production of imine and hydrogen peroxide (H 2 O 2 ) via photocatalytic aerobic amine oxidation is a bright way to obtain value added products, however, rapid recombination of photogenerated charge leads to low conversion efficiency and selectivity. Herein, a metal‐free amino acid modified hyper‐cross‐linked polymer (H 3 LP‐HCPs) photocatalyst was synthesized for photocatalytic amines oxidation by regulating the ratio of L‐phenylalanine (L‐Phe) and hexaphenylbenzene (Hex). The results showed that the H 3 LP‐HCPs photocatalyst with 1 : 3 molar ratio of L‐Phe and Hex achieves close to 100 % conversion efficiency and 100 % selectivity toward benzylamine oxidation under 455 nm blue LED lamp irradiation. Furthermore, a high yield of H 2 O 2 (9.2 mmol ⋅ g cat −1 ⋅ h −1 ) was synchronously obtained in benzylamine oxidation. Experiments and time‐dependent density functional theory calculation results revealed that the N‐functional groups in H 3 LP‐HCPs photocatalyst not only remarkably broadens light‐response range, but also facilitates electrons transfer from L‐Phe to the Hex, thus accelerating photogenerated charge separation efficiency and the formation of reactive oxygen species (ROS).