Integrating Suitable Linkage of Covalent Organic Frameworks into Covalently Bridged Inorganic/Organic Hybrids toward Efficient Photocatalysis

Covalent organic frameworks (COFs) are excellent platforms with tailored functionalities in photocatalysis. There are still challenges in increasing the photochemical performance of COFs. Therefore, we designed and prepared a series of COFs for photocatalytic hydrogen generation. Varying different ratios of β-ketoenamine to imine moieties in the linkages could differ the ordered structure, visible light harvesting, and bandgap. Overall, β-ketoenamine-linked COFs exhibited much better photocatalytic activity than those COFs having both β-ketoenamine and imine moieties on account of a nonquenched excited state and more favorable HOMO level in the photoinduced oxidation reaction from the former. Specifically, after in situ growth of β-ketoenamine-linked COFs onto NH2-Ti3C2Tx MXene via covalent connection, the heterohybrid showed an obvious improvement in photocatalytic H2 evolution because of strong covalent coupling, electrical conductivity, and efficient charge transfer. This integrated linkage evolution and covalent hybridization approach advances the development of COF-based photocatalysts.