Side-Chain Molecular Engineering of Triazole-Based Donor-Acceptor Polymeric Photocatalysts with Strong Electron Push-Pull Interactions

A new series of donor-acceptor (D-A)-type semiconductive polymers were generated by the integration of electron-deficient alkyl chain anchored triazole (TA) moieties and electron-rich pyrene units into the polymer skeleton. The polymer series demonstrated satisfactory light-harvesting ability and suitable band gaps. In the series, polymer P-TAME benefits from a minimized exciton binding energy, strongest D-A interaction, and favorable hydrophilicity, affording an outstanding photocatalytic H-2 evolution rate of ca. 100 mu mol h(-1) (10 mg polymer, AQY(420nm)=8.9%) and H2O2 production rate of ca. 190 mu mol h(-1) (20 mg polymer) under visible-light irradiation, which is superior to most currently reported polymers. All polymers in the series can mediate water oxidation reactions to evolve O-2. Thus, these TA-based polymers open up a new avenue toward tailor-made efficient photocatalysts with broad photocatalytic activities.