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

• Published in: Journal of the American Chemical Society 2021-12, Vol.143 (49), p.20792-20801
• Main Authors: Fu, Shanshan, Yao, Shuang, Guo, Song, Guo, Guang-Chen, Yuan, Wenjuan, Lu, Tong-Bu, Zhang, Zhi-Ming
• Format: Article
• Language: English
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.1c08908

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.