Donor–Acceptor Covalent–Organic Frameworks Based on Phthalimide as an Electron-Deficient Unit for Efficient Visible-Light Catalytic Hydrogen Evolution

Donor–acceptor two-dimensional covalent–organic frameworks (COFs) have great potential as photocatalysts for hydrogen evolution because of their tunable structures, ordered and strong stacking, high crystallinity, and porosity. Herein, an acceptor unit, namely phthalimide, has been employed for the first time to construct COFs. Two donor–acceptor COFs (TAPFy-PhI and TAPB-PhI) have been successfully synthesized via a Schiff base reaction using phthalimide as the acceptor and 1,3,6,8-tetrakis(4-aminophenyl)pyrene (TAPFy) and 1,3,5-tris(4-aminophenyl)benzene (TAPB) as donors. The synthesized COFs exhibited high crystallinity, permanent porosity, excellent chemical stability, suitable band gaps, and broad visible-light absorption. In the presence of ascorbic acid (sacrificial reagent), the TAPFy-PhI COF exhibited an efficient photocatalytic performance with a hydrogen evolution rate of 1763 μmol g–1 h–1. Moreover, the photocatalytic performance was further improved by the addition of Pt (1 wt %) as a cocatalyst, and the hydrogen evolution rate reached 2718 μmol g–1 h–1.