Robust Noble Metal-FreePhotoconversion of CO₂ to CO with a Molecule/MOF HybridCatalyst for StraightforwardTwo-Chamber Organic Carbonylation

Conversion of CO₂ is essential for advancing practical applications of photocatalytic CO₂ reduction. Herein, we report the application of robust CO₂ photoreduction in facilely handling CO-related organic synthesis through a two-chamber tandem reaction strategy. A noble metal-free molecule/metal–organic framework (MOF) hybrid catalyst composed of terpyridine-Fe(II) complex and MOF-808 was prepared for the photoconversion of CO₂ to CO with a yield of 731.7 mmol g^–1, a high selectivity of 99.0%, an apparent quantum yield of 23.6%, and a high CO₂ conversion of 93.7%. The superiority of the molecule/MOF hybrid catalyst and the interactions among the components in photocatalysis have been thoroughly investigated via a variety of experiments. Thanks to the rapid generation of sufficient CO and high CO₂ conversion, the photoreduction of CO₂ by the hybrid catalyst was further combined with Pd-catalyzed carbonylation reactions, generating a range of carbonyl compounds in good yields (65–96%). Additionally, sunlight-driven gram-scale synthesis of the bioactive compound moclobemide was achieved using photogenerated CO. This work showcases a hybridization method to develop high-performance MOF-based catalysts for CO₂ photoreduction and also illustrates the practical application of photogenerated CO in organic synthesis using CO₂ as a precursor.