Zn (II) Porphyrin Built-in D-A Covalent Organic Framework for Efficient Photocatalytic H 2 Evolution.

Covalent organic frameworks (COFs) with donor-acceptor (D-A) units are credible photocatalysts for their per-designed structure, inherent porosity, large surface area, splendid stability and so forth. Developing COFs with an excellent photocatalytic efficiency for hydrogen evolution is of a great significance in alleviating the energy crisis. Herein, a D-A type imine-linked crystalline Zn-Por-TT COF was fabricated successfully via the co-polymerization of electron-deficient Zinc (II) 5,10,15,20-tetrakis(para-aminophenyl) porphyrin (Zn-TAPP), and electron-rich thieno[3,2-b]thiophene-2,5-dicarbaldehyde (TT). Profiting from the D-A complex structure, the obtained Zn-Por-TT COF showcases an excellent photocatalytic activity with a hydrogen evolution rate of 8200 μmol/g/h, while the Zn-TAPP monomer presents practically no capacity for the generation of hydrogen under identical conditions. In addition, the counterparts Por-TT COF and COF-366-Zn were employed to illustrate the enhancement of the photocatalytic performance by metal catalytic sites and D-A structures. In addition, the counterparts Por-TT COF and COF-366-Zn were employed to illustrate the enhancement of metal catalytic sites and D-A structures for the photocatalytic performance.