Rational Design of Crystalline Covalent Organic Frameworks for Efficient CO2 Photoreduction with H2O

Abstract Solar energy‐driven conversion of CO 2 into fuels with H 2 O as a sacrificial agent is a challenging research field in photosynthesis. Herein, a series of crystalline porphyrin‐tetrathiafulvalene covalent organic frameworks (COFs) are synthesized and used as photocatalysts for reducing CO 2 with H 2 O, in the absence of additional photosensitizer, sacrificial agents, and noble metal co‐catalysts. The effective photogenerated electrons transfer from tetrathiafulvalene to porphyrin by covalent bonding, resulting in the separated electrons and holes, respectively, for CO 2 reduction and H 2 O oxidation. By adjusting the band structures of TTCOFs, TTCOF‐Zn achieved the highest photocatalytic CO production of 12.33 μmol with circa 100 % selectivity, along with H 2 O oxidation to O 2 . Furthermore, DFT calculations combined with a crystal structure model confirmed the structure–function relationship. Our work provides a new sight for designing more efficient artificial crystalline photocatalysts.