Carbazolic Conjugated Organic Polymers for Visible‐Light‐Driven CO 2 Photoreduction with H 2 O to CO with High Efficiency and Selectivity

Visible‐light‐driven CO 2 photoreduction with H 2 O to value‐added chemicals in high efficiency and selectivity is significant but challenging. Herein, a series of carbazolic conjugated organic polymers (CB‐COPs) with electron donor–acceptor (D–A) structures were prepared, which showed high efficiency for visible‐light‐driven photocatalytic reduction of CO 2 with H 2 O in a solid–gas mode, affording CO as the exclusive carbonaceous product. Especially, CB‐COP‐mpd derived from 3,5‐di(9 H ‐carbazol‐9‐yl)pyridine exhibited the highest CO evolution rate up to 191.46 μmol g −1 h −1 with a selectivity of 100 %. Mechanism studies showed that carbazolyl is a promising electron donor candidate for constructing CB‐COPs with D–A structures, capable of improving the catalytic efficiency and suppressing H 2 generation. The acceptor building block with excessive electron withdrawing capability was favorable to H 2 O adsorption, thus resulting in the generation of H 2 . This work provides new insights for designing COPs photocatalysts for CO 2 photocatalytic reduction.