Installing earth-abundant metal active centers to covalent organic frameworks for efficient heterogeneous photocatalytic CO2 reduction

Photocatalytic conversion of CO 2 into energy carriers has been recognized as a highly promising strategy for achieving the virtuous carbon cycle in nature. The realization of this process depends on an efficient catalyst to reduce the reaction barrier. Herein, we report a series of transition metal ion modified crystalline covalent organic frameworks (COFs) for the heterogeneous photocatalytic reduction of CO 2 . By coordinating different kinds of open metal active species into COFs, the resultant DQTP (2,6-diaminoanthraquinone - 2,4,6-triformylphloroglucinol) COF-M (M = Co/Ni/Zn) exerts a strong influence on the activity and selectivity of products (CO or HCOOH). Significantly, DQTP COF-Co exhibits a high CO production rate of 1.02 × 10 3 μmol h −1  g −1 , while DQTP COF-Zn has a high selectivity (90% over CO) for formic acid generation (152.5 μmol h −1  g −1 ). This work highlights the great potential of using stable COFs as platforms to anchor earth-abundant metal active sites for heterogeneous CO 2 reduction.