Electrostatic Attraction-Driven Assembly of a Metal–Organic Framework with a Photosensitizer Boosts Photocatalytic CO2Reduction to CO

Reducing CO2into fuels via photochemical reactions relies on highly efficient photocatalytic systems. Herein, we report a new and efficient photocatalytic system for CO2reduction. Driven by electrostatic attraction, an anionic metal–organic framework Cu-HHTP(HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) as host and a cationic photosensitizer [Ru(phen)3]2+(phen = 1,10-phenanthroline) as guest were self-assembled into a photocatalytic system Ru@Cu-HHTP, which showed high activity for photocatalytic CO2reduction under laboratory light source (CO production rate of 130(5) mmol g–1h–1, selectivity of 92.9%) or natural sunlight (CO production rate of 69.5 mmol g–1h–1, selectivity of 91.3%), representing the remarkable photocatalytic CO2reduction performance. More importantly, the photosensitizer [Ru(phen)3]2+in Ru@Cu-HHTPis only about 1/500 in quantity reported in the literature. Theoretical calculations and control experiments suggested that the assembly of the catalysts and photosensitizers via electrostatic attraction interactions can provide a better charge transfer efficiency, resulting in high performance for photocatalytic CO2reduction.