articleJournal of the American Chemical SocietySep 7, 2020Closed access

Regulating Photocatalysis by Spin-State Manipulation of Cobalt in Covalent Organic Frameworks

University of Science and Technology of China · Hefei National Center for Physical Sciences at Nanoscale · +4 more institutions

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Abstract

While catalysis is highly dependent on the electronic structure of the catalyst, the understanding of catalytic performance affected by electron spin regulation remains challenging and rare. Herein, we have developed a facile strategy to the manipulation of the cobalt spin state over covalent organic frameworks (COFs), COF-367-Co, by simply changing the oxidation state of Co centered in the porphyrin. Density functional theory (DFT) calculations together with experimental results confirm that CoII and CoIII are embedded in COF-367 with S = 1/2 and 0 spin ground states, respectively. Remarkably, photocatalytic CO2 reduction results indicate that COF-367-CoIII exhibits favorable activity and significantly…

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