Fully Conjugated Benzobisoxazole-Bridged Covalent Organic Frameworks for Boosting Photocatalytic Hydrogen Evolution.

2D covalent organic frameworks (2D-COFs) have attracted extensive interest in solar energy to hydrogen conversion. However, insufficient light harvesting and difficult exciton dissociation severely limit the improvement of photocatalytic activity for COFs, thereby impeding the progression of this advanced field. In this work, two benzobisoxazole-bridged and fully conjugated 2D-COFs with triazine (COF-JLU44) and pyrene (COF-JLU45) units were constructed for the first time via Knoevenagel polycondensation, and they hold long-range ordered structures, largely acceptable surface area, and fascinating photoelectric properties. Significantly, COF-JLU45 exhibits an impressive hydrogen evolution rate of 272.5 mmol g h and superior reusability in the presence of 1.0 wt% Pt under light irradiation, coupled with a remarkable apparent quantum yield of 12.9% at a long wavelength of 600 nm. Multiple spectroscopy and theoretical simulation demonstrate the ingenious design of COF-JLU45 widen its light absorption and effectively promote the exciton dissociation. This finding contributes valuable insights for constructing metal-free photocatalysts for solar energy conversion and utilization.