Regulating Charge Carrier Dynamics in Stable Perovskite Nanorods for Photo‐Induced Atom Transfer Radical Polymerization

Abstract Semiconducting nanocrystals have attracted world‐wide research interest in artificial photosynthesis due to their appealing properties and enticing potentials in converting solar energy into valuable chemicals. Compared to 0D nanoparticles, 1D nanorods afford long‐distance charge carriers separation and extended charge carriers lifetime due to the release of quantum confinement in axial direction. Herein, stable CsPbBr₃ nanorods of distinctive dimensions are crafted without altering their properties and morphology via grafting hydrophobic polystyrene (PS) chains through a post‐synthesis ligand exchange process. The resulting PS‐capped CsPbBr₃ nanorods exhibit a series of enhanced stabilities against UV irradiation, elevated temperature, and polar solvent, making them promising candidates for photo‐induced atom transfer radical polymerization (ATRP). Tailoring the surface chemistry and dimension of the PS‐capped CsPbBr₃ nanorods endows stable, but variable reaction kinetics in the photo‐induced ATRP of methyl methacrylate. The trapping‐detrapping process of photogenerated charge carriers lead to extended lifetime of charge carriers in lengthened CsPbBr₃ nanorods, contributing to a facilitated reaction kinetics of photo‐induced ATRP. Therefore, by leveraging such stable PS‐capped CsPbBr₃ nanorods, the effects of surface chemistry and charge carriers dynamics on its photocatalytic performance are scrutinized, providing fundamental understandings for designing next‐generation efficient nanostructured photocatalyst in artificial photosynthesis and solar energy conversion.