Photoelectron Transfer Mediated by the Interfacial Electron Effectsfor Boosting Visible-Light-Driven CO2 Reduction br

Imine-linked covalent organic frameworks (COFs) are popularcandidates for photocatalytic CO2reduction, but high polarization of theimine bond is less efficient for pi-electron delocalization between the linkedbuilding units, leading to low intramolecular electron transfer and poorphotocatalytic efficiency. Herein, we present a structural and electronicengineering strategy through integrating the imine-linked COF consisting ofZn-porphyrin and Co-bipyridyl units with cadmium sulfide (CdS)nanowires to form a CdS@COF core-shell structure. The experimental andtheoretical results have validated that CdS serves as the electron transferchannel through the interfacial electron effects, which induces photoelectrontransfer from Zn-porphyrin to CdS and subsequent injection into Co-bipyridyl units for CO2reduction. The as-prepared CdS@COF generates4057 mu mol g-1CO in 8 h under visible-light irradiation, which is considerablyhigher than those of its neat CdS and imine-linked COF counterparts. This work provides protocols to tackle intramolecular chargetransfer across polar linkages between photosensitizers and active sites for solar-to-chemical energy conversion