Substituent Effects on the Photocatalytic Properties of a Symmetric Covalent Organic Framework

Ting-Ting Liu; Xin-Ping Wu; Xue-Qing Gong

doi:10.1063/1674-0068/cjcp2205088

Volume 35 Issue 4

Aug. 2022

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Ting-Ting Liu, Xin-Ping Wu, Xue-Qing Gong. Substituent Effects on the Photocatalytic Properties of a Symmetric Covalent Organic Framework[J]. Chinese Journal of Chemical Physics , 2022, 35(4): 647-654. doi: 10.1063/1674-0068/cjcp2205088

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Ting-Ting Liu, Xin-Ping Wu, Xue-Qing Gong. Substituent Effects on the Photocatalytic Properties of a Symmetric Covalent Organic Framework[J]. Chinese Journal of Chemical Physics , 2022, 35(4): 647-654. doi: 10.1063/1674-0068/cjcp2205088

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Substituent Effects on the Photocatalytic Properties of a Symmetric Covalent Organic Framework

doi: 10.1063/1674-0068/cjcp2205088

Key Laboratory for Advanced Materials and Joint International Research Laboratory for Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Centre for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China

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Corresponding author: Xin-Ping Wu, E-mail: xpwu@ecust.edu.cn; Xue-Qing Gong, E-mail: xgong@ecust.edu.cn
Received Date: 2022-05-13
Accepted Date: 2022-06-14
Publish Date: 2022-08-27

Abstract

Abstract

Symmetric covalent organic framework (COF) photocatalysts generally suffer from inefficient charge separation and short-lived photoexcited states. By performing density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations, we find that partial substitution with one or two substituents (N or NH$_2$) in the linkage of the representative symmetric COF (N$_0$-COF) gives rise to the separation of charge carriers in the resulting COFs (\emph{i.e}., N$_1$-COF, N$_2$-COF, (NH$_2$)$_1$-N$_0$-COF, and (NH$_2$)$_2$-N$_0$-COF). Moreover, we also find that the energy levels of the highest occupied crystal orbital (HOCO) and the lowest unoccupied crystal orbital (LUCO) of the N$_0$-COF can shift away from or toward the vacuum level, depending on the electron-withdrawing or electron-donating characters of the substituent. Therefore, we propose that partial substitution with carefully chosen electron-withdrawing or electron-donating substituents in the linkages of symmetric COFs can lead to efficient charge separation as well as appropriate HOCO and LUCO positions of the generated COFs for specific photocatalytic reactions. The proposed rule can be utilized to further boost the photocatalytic performance of many symmetric COFs.
- Covalent organic framework,
- Photocatalysis,
- Electronic structure,
- Charge separation,
- Density functional theory calculation

^† Part of Special Topic "the 1st Young Scientist Symposium on Computational Catalysis".

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References(40)

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