Impact of the Donor–Acceptor Structure on PhotocatalyticHydrogen Generation by Polyfluorene Polymer Dots

Organic semiconductor polymers have garnered significant attention within the realm of photocatalytic hydrogen generation. Researchers have designed numerous schemes to enhance the efficiency of hydrogen generation by leveraging the tunable properties of their main chains. The donor–acceptor (D–A) strategy is a recognized approach for tuning the photoelectric properties of polymer semiconductors; however, its application within organic photocatalytic hydrogen generation demands thorough investigation. Here, we use the polyfluorene derivatives to study the effect of the D–A structure on hydrogen generation properties. After these polymers were prepared into polymer dots (Pdots) through the nanoprecipitation method, they exhibited excellent hydrogen generation properties. We found that PFO-Pdots obtained a hydrogen generation rate of 0.74 mmol g^–1 h^–1, and PFBT-Pdots with the D–A structure had about three times the hydrogen generation rate (2.23 mmol g^–1 h^–1) of PFO-Pdots, while PFVA-Pdots in the presence of the D–D structure obtained only one-half of the hydrogen generation rate (0.34 mmol g^–1 h^–1) of PFO-Pdots. These results indicated that the D–A structure plays a critical role in enhancing the photocatalytic hydrogen generation performance of organic semiconductor polymers. This will motivate organic polymers to take advantage of their structural tunability and enable further development in the field of photocatalytic hydrogen generation.