Visible‐Light‐Driven MADIX Polymerisation via a Reusable,Low‐Cost,and Non‐Toxic Bismuth Oxide Photocatalyst

The continuous amalgamation of photocatalysis into existing reversible deactivation radical polymerisation (RDRP) processes has initiated a rapidly propagating area of polymer research in recent years. We introduce bismuth oxide (Bi₂O₃) as a heterogeneous photocatalyst for polymerisations, operating at room temperature with visible light. We demonstrate formidable control over degenerative chain‐transfer polymerisations, such as macromolecular design by interchange of xanthate (MADIX) and reversible addition‐fragmentation chain‐transfer (RAFT) polymerisation. We achieved narrow molecular weight distributions and attribute the excellent temporal control of a photo‐induced electron transfer (PET) process. This methodology was employed to synthesise diblock copolymers combining differently activated monomers. The Bi₂O₃ catalyst system has the additional benefits of low toxicity, reusability, low‐cost, and ease of removal from the reaction mixture.