Reversing Surface Charge for Highly‐Active Organic Photovoltaic Catalysts

Organic photovoltaic materials typically exhibit low charge separation and transfer efficiency and severe exciton/carrier recombination due to high exciton binding energy and short exciton diffusion lengths, limiting the enhancement of photocatalytic hydrogen evolution performance. Here, we introduce a surface charge reversal strategy to regulate charge characters of organic photovoltaic catalyst (OPC). Compared to OPC nanoparticles (NPs) stabilized by anionic surfactant ((−) NPs), NPs stabilized by cationic surfactant ((+) NPs) exhibit a raised Fermi level, larger surface band bending and Schottky barrier, thereby enhancing charge separation and transfer efficiency while suppressing charge carrier recombination. As result, (+) NPs demonstrate better photocatalytic performance than (−) NPs, independent of the chemical structure of OPCs and surfactant molecules. Under illumination of AM1.5G, 100 mW cm‐2, the PM6: 2FBP‐4F NPs stabilized by cationic surfactant (dodecyltrimethylammonium bromide, DTAB) exhibit much higher photocatalytic activity for hydrogen evolution (up to 946.1±15.76 mmol h‐1 g‐1) than that of PM6: 2FBP‐4F NPs stabilized by anionic surfactant, among the best results reported so far for photocatalytic hydrogen evolution under simulated sunlight.