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.

Automated summary

A new series of semiconductive polymers with donor-acceptor (D-A) structure were synthesized, incorporating electron-deficient alkyl chain anchored triazole (TA) moieties and electron-rich pyrene units. The polymers exhibited satisfactory light-harvesting ability and suitable band gaps. Among them, polymer P-TAME showed remarkable photocatalytic performance, achieving high hydrogen evolution rate and hydrogen peroxide production rate under visible-light irradiation, surpassing most reported polymers. Furthermore, all polymers in the series demonstrated water oxidation activity, evolving oxygen. These TA-based polymers offer a new avenue for tailoring efficient photocatalysts with broad photocatalytic activities.