Poly(ionic liquid)s for Photo‐Driven CO2 Cycloaddition: Electron Donor–Acceptor Segments Matter

Abstract CO 2 cycloaddition with epoxides is a key catalytic procedure for CO 2 utilization. Several metal‐based catalysts with cocatalysts are developed for photo‐driven CO 2 cycloaddition, while facing difficulties in product purification and continuous reaction. Here, poly(ionic liquid)s are proposed as metal‐free catalysts for photo‐driven CO 2 cycloaddition without cocatalysts. A series of poly(ionic liquid)s with donor–acceptor segments are fabricated and their photo‐driven catalytic performance (conversion rate of 83.5% for glycidyl phenyl ether) outstrips (≈4.9 times) their thermal‐driven catalytic performance (17.2%) at the same temperature. Mechanism studies confirm that photo‐induced charge separation is promoted by the donor–acceptor segments and can accelerate the CO 2 cycloaddition reaction. This work paves the way for the further use of poly(ionic liquid)s as catalysts in photo‐driven CO 2 cycloaddition.