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Halogen modified two-dimensional covalent triazine frameworks as visible-light driven photocatalysts for overall water splitting

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Abstract

The covalent triazine framework CTF-1 as a member of the two-dimensional covalent organic frameworks (COFs) is a category of novel metal-free photocatalysts for water splitting. The large band gap severely restricts its energy conversion efficiency. By means of the first-principles calculations, we proposed the decoration of CTF-1 by anchoring halogen atoms onto benzene moieties for improving the solar-to-hydrogen (STH) efficiency. The electronic structures reveal that the halogen substitution successfully decreases the band gap of CTF-1. Meanwhile, the calculated free energy changes along the reaction pathway indicate that all these COFs can spontaneously drive overall water splitting under light irradiation in a specific acid-base environment. The time-dependent ab initio non-adiabatic molecular dynamics simulations suggest that the electron-hole recombination periods of these COFs fall in a few to tens of nanoseconds. Excitingly, CTF-1 modified by linking six iodine atoms onto the benzene ring in the para-position (CTF-1-6I) shows a quite low band gap of 2.81 eV, indicating that it is a visible-light driven COF for overall photocatalytic water splitting. Correspondingly, CTF-1-6I also exhibits an extraordinarily promising STH efficiency of 3.70%, which is an order magnitude higher than that of the pristine CTF-1.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21688102), the National Key Research and Development Program of China (2016YFA0200604), and Anhui Initiative in Quantum Information Technologies (AHY090400). The numerical calculations have been done on the supercomputing system in the Super-computing Center of University of Science and Technology of China and Supercomputing Center of Chinese Academy of Sciences.

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Authors and Affiliations

  1. Hefei National Laboratory of Physical Science at the Microscale, Department of Chemical Physics, Synergetic Innovation Center of Quantum Information & Quantum Physics, University of Science and Technology of China, Hefei, 230026, China

    Cen-Feng Fu, Chuanyu Zhao, Qijing Zheng, Xingxing Li, Jin Zhao & Jinlong Yang

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  1. Cen-Feng Fu
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  2. Chuanyu Zhao
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  3. Qijing Zheng
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  4. Xingxing Li
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  5. Jin Zhao
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  6. Jinlong Yang
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Correspondence to Jinlong Yang.

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Halogen modified two-dimensional covalent triazine frameworks as visible-light driven photocatalysts for overall water splitting

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Fu, CF., Zhao, C., Zheng, Q. et al. Halogen modified two-dimensional covalent triazine frameworks as visible-light driven photocatalysts for overall water splitting. Sci. China Chem. 63, 1134–1141 (2020). https://doi.org/10.1007/s11426-020-9766-5

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