Covalent Organic Frameworks for Photocatalytic Reduction of Carbon Dioxide: A Review

Covalent organic frameworks (COFs) are crystalline networks with extended backbones cross-linked by covalent bonds. Due to the semiconductive properties and variable metal coordinating sites, along with the rapid development in linkage chemistry, the utilization of COFs in photocatalytic CO₂RR has attracted many scientists' interests. In this Review, we summarize the latest research progress on variable COFs for photocatalytic CO₂ reduction. In the first part, we present the development of COF linkages that have been used in CO₂RR, and we discuss four mechanisms including COFs as intrinsic photocatalysts, COFs with photosensitive motifs as photocatalysts, metalated COF photocatalysts, and COFs with semiconductors as heterojunction photocatalysts. Then, we summarize the principles of structural designs including functional building units and stacking mode exchange. Finally, the outlook and challenges have been provided. This Review is intended to give some guidance on the design and synthesis of diverse COFs with different linkages, various structures, and divergent stacking modes for the efficient photoreduction of CO₂.