Covalent Organic Framework‐Semiconductor‐Based Heterostructures for Photocatalytic Applications

Abstract Photocatalysis is a promising and sustainable technology in the fields of energy conversion/storage and environment purification; however, the utilization of individual component as photocatalyst is generally restricted due to the low catalytic activity deriving from the rapid recombination of photogenerated electrons/holes. Covalent organic framework (COF)‐semiconductor‐based composite photocatalysts with synergistic effects provide a feasible route to achieve high‐performance photocatalytic reactions with more active sites, strong light utilization ability, and high stability. In recent years, significant progress has been made in the rational design and preparation of the COF‐semiconductors‐based heterostructures for photocatalytic water splitting, carbon dioxide (CO 2 ) reduction, and dye/pollutant degradation. In this Review, the synthetic strategies of COF‐semiconductor‐based heterostructures are first introduced, which includes the rational design of the morphology, connection modes, and type of heterojunctions. The performance of COF‐semiconductor‐based heterostructures in different photocatalytic reactions are comprehensively reviewed. The structure‐activity relationship and the synergistic effects within the heterostructures are discussed, and the photocatalytic mechanism and the role of COFs during the photocatalytic process are also presented. Finally, an outlook and challenges of realizing COF‐semiconductor‐based heterostructures with simple synthesis methods, diverse functions, high performance, and well‐defined reaction mechanisms are provided.