Sulfone-containing covalent organic frameworks for photocatalytic hydrogen evolution from water

• DOI: 10.1038/s41557-018-0141-5
• Publication Date: 2018-09-24T09:55:37Z
• Authors: Xiaoyan Wang; Linjiang Chen; Samantha Y. Chong; Marc A. Little; Yongzhen Wu; Wei-Hong Zhu; Rob Clowes; Yong Yan; Martijn A. Zwijne...; Reiner Sebastian ...; Andrew I. Cooper
• Keywords: Benzothiophene; Covalent organic framework; Moiety

Nature uses organic molecules for light harvesting and photosynthesis, but most man-made water splitting catalysts are inorganic semiconductors. Organic photocatalysts, while attractive because of their synthetic tunability, tend to have low quantum efficiencies for water splitting. Here we present a crystalline covalent organic framework (COF) based on a benzo-bis(benzothiophene sulfone) moiety that shows a much higher activity for photochemical hydrogen evolution than its amorphous or semicrystalline counterparts. The COF is stable under long-term visible irradiation and shows steady photochemical hydrogen evolution with a sacrificial electron donor for at least 50 hours. We attribute the high quantum efficiency of fused-sulfone-COF to its crystallinity, its strong visible light absorption, and its wettable, hydrophilic 3.2 nm mesopores. These pores allow the framework to be dye-sensitized, leading to a further 61% enhancement in the hydrogen evolution rate up to 16.3 mmol g-1 h-1. The COF also retained its photocatalytic activity when cast as a thin film onto a support.