Electronic Transmission Channels Promoting Charge Separation of Conjugated Polymers for Photocatalytic CO ₂ Reduction with Controllable Selectivity

Conjugated polymers (CPs) represent a promising platform for photocatalytic CO 2 fixation owing to their suitable band structures that meet the requirements of the reduction potential of CO 2 to value‐added fuels. However, the photocatalytic performance of CPs is rather restrained by the low charge transfer efficiency. Herein, we rationally designed three CPs with a more delocalized electronic transmission channel and planar molecular structure, which are regarded to evidently reduce the exciton binding energy (E b ) and accelerate the internal charge transfer process. Besides, the assembly of suitable electron‐output “tentacles” and cocatalysts on the surface of CPs could effectively facilitate interfacial electron delivery. Accordingly, the optimal P‐2CN exhibits an apparent quantum yield of 4.6 % at 420 nm for photocatalytic CO 2 to CO. Further adjusting the amounts of cyano groups and cocatalysts, the CO selectivity could be obtained in the range of 0–80.5 %.