Impact of Imine Bond Orientations and Acceptor Groups on Photocatalytic Hydrogen Generation of Donor-Acceptor Covalent Organic Frameworks

Covalent organic frameworks (COFs) have emerged as one of the most studied photocatalysts owing to their adjustable structure and bandgaps. However, there is limited research on regulating the light-harvesting capabilities of acceptor building blocks in donor-acceptor (D-A) isomer COFs with different bond orientations. This investigation is crucial for elucidating the structure-property-performance relationship of COF photocatalysts. Herein, a series of D-A isostructural COFs are synthesized with different imine bond orientations using benzothiadiazole and its derivatives-based organic building units. Extended light absorption is achieved in COFs with acceptor groups that have strong electron-withdrawing capacities, although this resulted a decreased hydrogen generation efficiency. Photocatalytic experiments indicated that dialdehyde benzothiadiazole-based COFs, HIAM-0015, exhibit the highest hydrogen generation rate (17.99 mmol g-1 h-1), which is 15 times higher than its isomer. The excellent photocatalytic performance of HIAM-0015 can be attributed to its fast charge separation and migration. This work provides insights into the rational design and synthesis of D-A COFs to achieve efficient photocatalytic activity. Six iso-structural COFs are designed and synthesized to explore light-absorption range and bond orientation effect on the photocatalytic performance in D-A COFs. The results indicate that imine bond orientation has a significant effect on the photocatalytic performance, however, extended light-absorption is not the decisive factor to achieve efficient photocatalytic activity. image