Spatial Regulation of Acceptor Units in Olefin-Linked COFs toward Highly Efficient Photocatalytic H₂ Evolution

Covalent organic frameworks (COFs)-based photocatalysts have received growing attention for photocatalytic hydrogen (H₂ ) production. One of the big challenges in the field is to find ways to promote energy/electron transfer and exciton dissociation. Addressing this challenge, herein, a series of olefin-linked 2D COFs is fabricated with high crystallinity, porosity, and robustness using a melt polymerization method without adding volatile organic solvents. It is found that regulation of the spatial distances between the acceptor units (triazine and 2, 2'-bipyridine) of COFs to match the charge carrier diffusion length can dramatically promote the exciton dissociation, hence leading to outstanding photocatalytic H₂ evolution performance. The COF with the appropriate acceptor distance achieves exceptional photocatalytic H₂ evolution with an apparent quantum yield of 56.2% at 475 nm, the second highest value among all COF photocatalysts and 70 times higher than the well-studied polymer carbon nitride. Various experimental and computation studies are then conducted to in-depth unveil the mechanism behind the enhanced performance. This study will provide important guidance for the design of highly efficient organic semiconductor photocatalysts.