Amphiphilic Polycarbonate Micellar Rhenium Catalysts for Efficient Photocatalytic CO₂ Reduction in Aqueous Media

A triblock amphiphilic polymer derived from the copolymerization of CO 2 and epoxides containing a bipyridine rhenium complex in its backbone is shown to effectively catalyze the visible‐light‐driven reduction of CO 2 to CO. This polymer provides uniformly spherical micelles in aqueous solution, where the metal catalyst is sequestered in the hydrophobic portion of the nanostructured micelle. CO 2 to CO reduction occurs in an efficient visible‐light‐driven process in aqueous media with turnover numbers up to 110 (>99 % selectivity) in the absence of a photosensitizer, which is a 37‐fold enhancement over the corresponding molecular rhenium catalyst in organic solvent. Notably, the amphiphilic polycarbonate micelle rhenium catalyst suppresses H 2 generation, presumably by preventing deactivation of the active catalytic center by water.