Affiliation:
1. CAS Key Laboratory of Design and Assembly of Functional Nanostructures Fujian Provincial Key Laboratory of Nanomaterials State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences Fuzhou 350002 Fujian P. R. China
2. University of Chinese Academy of Sciences Beijing 100049 P. R. China
3. Fujian Science and Technology Innovation Laboratory for Optoelectronic Information of China Fuzhou 350108 Fujian P. R. China
4. Fuzhou University Fuzhou 350108 Fujian P. R. China
Abstract
AbstractPhotocatalytic oxygen reduction to produce hydrogen peroxide (H2O2) is a promising route to providing oxidants for various industrial applications. However, the lack of well‐designed photocatalysts for efficient overall H2O2 production in pure water has impeded ongoing research and practical thrusts. Here we present a cyanide‐based covalent organic framework (TBTN‐COFs) combining 2,4,6‐trimethylbenzene‐1,3,5‐tricarbonitrile (TBTN) and benzotrithiophene‐2,5,8‐tricarbaldehyde (BTT) building blocks with water‐affinity and charge‐separation. The ultrafast intramolecular electron transfer (<500 fs) and prolonged excited state lifetime (748 ps) can be realized by TBTN‐COF, resulting in a hole accumulated BTT and electron‐rich TBTN building block. Under one sun, the 11013 μmol h−1 g−1 yield rate of H2O2 can be achieved without any sacrificial agent, outperforming most previous reports. Furthermore, the DFT calculation and in situ DRIFTS spectrums suggesting a Yeager‐type absorption of *O2⋅− intermediate in the cyanide active site, which prohibits the formation of superoxide radical and revealing a favored H2O2 production pathway.
Funder
National Natural Science Foundation of China