Robust Noble Metal-Free Photoconversion of CO₂ to CO with a Molecule/MOF Hybrid Catalyst for Straightforward Two-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.