Solution-Processable Donor-Acceptor Copolymer Thin Films for Efficient Visible-Light-Driven Photocatalytic Hydrogen Evolution

Conjugated polymers (CPs) have been actively utilized as photocatalysts for hydrogen evolution due to their easy synthetic tunability to endow specific functionalities, including visible-light absorption, higher-lying LUMO energy for proton reduction, and sufficient photochemical stability. Enhancing interfacial surface and compatibility of hydrophobic CPs with hydrophilic water is the central focus to improve the hydrogen evolution rate (HER). Although a number of successful approaches have been developed in recent years, tedious chemical modifications or post-treatment of CPs make reproducibility of the materials difficult. In this work, a solution processable PBDB-T polymer is directly deposited on a glass substrate to form a thin film that is immersed in an aqueous solution to photochemically catalyze H₂ generation. The PBDB-T thin film showed a much higher hydrogen evolution rate (HER) than the typical method of using PBDB-T suspended solids due to the enhanced interfacial area with a more suitable solid-state morphology. When the thickness of the thin film is reduced to dramatically improve the utilization of the photocatalytic material, the 0.1 mg-based PBDB-T thin film exhibited an unprecedentedly high HER of 120.90