Feeding Carbonylation with CO₂ via the Synergy of Single-Site/Nanocluster Catalysts in a Photosensitizing MOF

Solar-driven carbonylation with CO₂ replacing toxic CO as a C1 source is of considerable interest; however it remains a great challenge due to the inert CO₂ molecule. Herein, we integrate cobalt single-site and ultrafine CuPd nanocluster catalysts into a porphyrin-based metal–organic framework to construct composite photocatalysts (Cu₁Pd₂)_z@PCN-222­(Co) (z = 1.3, 2.0, and 3.0 nm). Upon visible light irradiation, excited porphyrin can concurrently transfer electrons to Co single sites and CuPd nanoclusters, providing the possibility for coupling CO₂ photoreduction and Suzuki/Sonogashira reactions. This multicomponent synergy in (Cu₁Pd₂)_1.3@PCN-222­(Co) can not only replace dangerous CO gas but also dramatically promote the photosynthesis of benzophenone in CO₂ with over 90% yield and 97% selectivity under mild condition. Systematic investigations clearly decipher the function and collaboration among different components in these composite catalysts, highlighting a new insight into developing a sustainable protocol for carbonylation reactions by employing greenhouse gas CO₂ as a C1 source.