2017 J. Am. Chem. Soc., 2017, 139, 356.
Materials development for artificial photosynthesis, in particular CO2 reduction, has been under extensive efforts, ranging from inorganic semiconductors to molecular complexes. In this report, we demonstrate a metal-organic framework (MOF) coated nanoparticle photocatalyst with enhanced CO2 reduction activity and stability, which stems from having two different functional units for activity enhancement and catalytic stability combined together as a single construct. Covalently attaching a CO2-to-CO conversion photocatalyst ReI(CO)3(BPYDC)Cl, BPYDC = 2,2’-bipyridine-5,5’–dicarboxylate, to a zirconium MOF, UiO-67 (Ren-MOF), prevents dimerization leading to deactivation. By systematically controlling its density in the framework (n = 0, 1, 2, 3, 5, 11, 16, and 24 complexes per unit cell), the highest photocatalytic activity was found for Re3-MOF. Structural analysis of Ren-MOFs suggest that a fine balance of proximity between photoactive centers is needed for cooperatively enhanced photocatalytic activity, where an optimum number of Re complexes per unit cell should reach the highest activity. Based on the structure-activity correlation of Ren-MOFs, Re3-MOF was coated onto Ag nanocubes (AgRe3-MOF), which spatially confined photoactive Re centers to the intensified near-surface electric fields at the surface of Ag nanocubes, resulting in a seven-fold enhance-ment of CO2-to-CO conversion under visible light with long-term stability maintained up to 48 hours.