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

Xiaoyan Wang, Linjiang Chen, Samantha Y. Chong, Marc A. Little, Yongzhen Wu, Hong-Wei Zhu, Rob Clowes, Yong Yan, Martijn A. Zwijnenburg, Reiner Sebastian Sprick, Andrew I. Cooper*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

860 Citations (Scopus)


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.
Original languageEnglish
Pages (from-to)1180-1189
Number of pages10
JournalNature Chemistry
Publication statusPublished - Dec 2018


  • materials chemistry
  • photocatalysis

ASJC Scopus subject areas

  • General Chemistry
  • General Chemical Engineering


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