Insight into the role of graphene quantum dots on the boosted photocatalytic H2 production performance of a covalent organic framework

[Display omitted] •An entirely novel kind of GQDs-modified TpPa-1-COF photocatalyst was prepared.•GQDs were synchronously deposited onto the TpPa-1-COF by the in-situ method.•GQDs serve as a photosensitizer that enhances the optical absorption ability.•The 0.44% GQDs/TpPa-1-COF shows a better H2 production than bare COF by 2.9 times.•DFT simulation indicates the highly efficient interfacial charge migration. The photocatalytic activity of covalent organic frameworks (COFs) to evolve hydrogen (H2) triggered by visible light has been promising, but the separation and migration efficiency of photogenerated electron-hole pairs still have to be improved. In the study, we designed and synthesized a kind of graphene quantum dots (GQDs) modified β-ketoenamine-linked COF composite (GQDs/COF) by an in-situ method to improve its photocatalytic H2 evolution for the first time. The resulting 0.44% GQDs/TpPa-1-COF shows a rate of H2 production of 487 μmol g−1h−1 with the illumination of visible light, outperforming those of bare TpPa-1-COF by 2.9 times. It is found that the GQDs serve as a photosensitizer that effectively enhances the optical absorption ability. Moreover, GQDs serve as a means of collecting photoinduced electrons as for preventing the subsequent recombination of carriers excited by visible light. Furthermore, the Ohmic contact effect between the TpPa-1-COF and GQDs facilitates the highly efficient migration of photoinduced electrons, which has been demonstrated by the density functional theory (DFT) calculation results. Overall, this work provides a novel strategy to design COF-based composites and gives some insight into the role of GQDs on enhanced photocatalytic activity.