Rational Construction of Donor–Acceptor Covalent Organic Framework Heterojunction for High-Performance Photocatalytic Production of H2O2

H2O2 production via dual channels based on both the oxygen reduction reaction (ORR) and water oxidation reaction (WOR) remains significantly challenging while meaningful. Here, we rationally constructed electron donor–acceptor COFs@COFs, i.e., D@A-COF, by in situ growth of electron-acceptor COF (A-COF) on electron-donor COF (D-COF) for efficient H2O2 production according to the synergetic donor–acceptor (D–A) and heterojunction strategies. A specific S-scheme of heterojunction was formed favorably at the boundary, and the stable C═N covalent bonds connected D-COF and A-COF, and hence as-prepared D@A-COF exhibited a wider light range, stronger absorption, and faster electron–hole separation and transfer ability than the primitive COFs. Impressively, the photocatalytic H2O2 production rate of D@A-COF was up to 5462 μmol h–1 g–1, significantly higher than the counterpart D-COF (325 μmol h–1 g–1), A-COF (1860 μmol h–1 g–1), D-A-COF-1 (657 μmol h–1 g–1), and D-A-COF-2 (201 μmol h–1 g–1). The results showed that the overall photocatalytic production of H2O2 by D@A-COF was carried out simultaneously through dual channels of the ORR and WOR, and the ORR likely occurred in D-COF, while the WOR was mostly located in A-COF. This work highlights the rational construction of donor–acceptor COFs@COFs heterojunction, providing unique insight into efficient photocatalysts for H2O2 production.