Keto-enamine-based covalent organic framework with controllable anthraquinone moieties for superior H2O2 photosynthesis from O2 and water

Photocatalytic H2O2 production is a promising strategy for decentralized applications, but to realize efficient H2O2 production in the ambient conditions and absence of organic sacrifice remains challengeable. Herein, anthraquinone functionalized covalent organic frameworks (TpAQ-COFs) were fabricated by β-ketoenamines links of 2,6-diaminoanthraquinone (AQ) and 2, 4, 6-triformylphloroglucinol (Tp), and the structures and compositions were tuned by controlling the condensation time. The increase of time favors the assembly of TpAQ-COFs into more ordered lamellar stacking structure, and induces the increase of enol-imine form. The critical role of anthraquinone moieties as the active sites for oxygen reduction was proved, that is, facilitating charge separation and enhancing the activity and selectivity of H2O2 production. Upon visible light irradiation, the TpAQ-COF synthesized after 12 h reaction has the highest content of anthraquinone moieties and the best performance for H2O2 production (420 μmol h−1 g−1) in the absence of organic sacrificial agents. These findings bring insights to incorporate anthraquinone chemistry into photocatalysts at molecular levels for efficient H2O2 production.