Heterogenization of Salen Metal Molecular Catalysts in Covalent Organic Frameworks for Photocatalytic Hydrogen Evolution.

Integrating a molecular catalyst with a light harvester into a photocatalyst is an effective strategy for solar light conversion. However, it is challenging to establish a crystallized framework with well-organized connections that favour charge separation and transfer. Herein, we report the heterogenization of a Salen metal complex molecular catalyst into a rigid covalent organic framework (COF) through covalent linkage with the light-harvesting unit of pyrene for photocatalytic hydrogen evolution. The chemically conjugated bonds between the two units contribute to fast photogenerated electron transfer and thereby promote the proton reduction reaction. The Salen cobalt-based COF showed the best hydrogen evolution activity (1378 µmol g-1 h-1 ), which is superior to the previously reported nonnoble metal based COF photocatalysts. This work provides a strategy to construct atom-efficient photocatalysts by the heterogenization of molecular catalysts into covalent organic frameworks.