Rational design of D− π − A− π − D porous organic polymer with polarized π for photocatalytic aerobic oxidation
Applied Catalysis B: Environmental(2023)
摘要
Charge separation and reactive oxygen species (ROS) generation efficiency are of foremost importance for photocatalytic aerobic oxidation reactions. In this study, four porous organic polymers (POPs), namely JNU-208, -209, -210, and -211, were designed and synthesized from linear bipyrazoles and cyanuric chloride through condensation reactions. The donor−acceptor−donor (D−A−D) type POP (JNU-209) exhibits improved photo-electrochemical properties relative to the donor–π–donor (D−π − D) type POP (JNU-208). Benzene and thiophene were further incorporated respectively as bridging π-units. The two corresponding D− π − A− π − D type POPs (JNU-210 and -211) exhibit additionally enhanced photo-electrochemical properties. The four POPs were examined their potentials as photocatalysts for the aerobic oxidation of benzylamines, and JNU-211 was found to have the highest photocatalytic activity. Theoretical calculations confirm that the introduction of thiophene not only increases the conjugation but also promotes the π-electron polarization, both of which facilitate charge separation and ROS generation.
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关键词
photocatalytic aerobic oxidation,porous organic polymer
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