Antimony-Based Halide Perovskite Nanoparticles as Lead-Free Photocatalysts for Controlled Radical Polymerization

Metal halide perovskites have emerged as versatile photocatalysts to convert solar energy for chemical processes. Perovskite photocatalyzed polymerization draws special attention due to its straightforward synthesis process and the ability to create advanced perovskite-polymer nanocomposites. Herein, this work employs Cs₃Sb₂Br₉ perovskite nanoparticles (NPs) as a lead-free photocatalyst for light-controlled atom transfer radical polymerization (ATRP). Cs₃Sb₂Br₉ NPs exhibit high reduction potential and interact with electronegative bromide initiator with Lewis acid Sb sites, enabling efficient photoinduced reduction of initiators and controlled polymerization under blue light irradiation. Methacrylate monomers with various functional groups are successfully polymerized, and the resulting polymer showcased a dispersity (Đ) as small as 1.27. The living nature of polymerization is confirmed by high chain end fidelity and kinetic studies. Moreover, Cs₃Sb₂Br₉ NPs serve as heterogeneous photocatalysts, demonstrating recyclability and reusability for up to four cycles. This work presents a promising approach to overcome the limitations of lead-based perovskites in photoinduced controlled radical polymerization, offering a sustainable and efficient alternative for the synthesis of well-defined polymeric materials.