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Regulating local polarization in truxenone-based covalent organic frameworks for boosting photocatalytic hydrogen evolution

调控三芴酮基共价有机框架中的局域极化促进光催化析氢活性

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Abstract

The high local charge delocalization and strong dipole moment are two key factors that affect the photocatalytic hydrogen evolution over covalent organic frameworks (COFs)-based photocatalysts. However, there is a scarcity of reports that systematically investigate the structure–function relationship of these factors based on precise structural models. Herein, this study proposes a novel strategy for evaluating local charge delocalization using three rationally designed truxenone-based COFs. By controlling the structure and dipole of the monomers at the molecular level, we aim to investigate the structure–function relationship of these COFs concerning local charge delocalization. Among the different truxenone-based COFs evaluated, 1,3,5-tris (p-formyl phenyl) benzene-based COF (TeTpb-COF) exhibits the highest hydrogen evolution rate of 21.6 mmol g−1 h−1, resulting in a 108-fold improvement in photocatalytic hydrogen evolution performance compared with that of 2,4,6-tris(4-formylphenyl)-1,3,5-triazine-based COF (TeTt-COF, 0.2 mmol g−1 h−1). This enhancement can be attributed to the strong intramolecular built-in electric field, which facilitates the efficient separation of photogenerated charges in the donor–acceptor (D–A) block units and increases the photoinduced charge migration distance and separation efficiency. This work highlights the strategy of adjusting the building blocks to enhance the local dipole moment in truxenone-based COFs, thereby significantly improving photocatalytic hydrogen evolution. The regulation of building blocks offers an opportunity to create a novel COF platform for high-efficiency photocatalytic hydrogen evolution.

摘要

局部电荷的强离域和强偶极矩是影响共价有机框架(COFs)基光催化剂催化析氢性能的两个关键因素. 然而, 基于精确的调控结构模型来系统研究这种构效关系的报告相对较少. 本研究提出了一种新的策略, 通过合理的设计, 制备了三种三芴酮基COFs, 通过在分子水平上调控单体的结构和偶极来提高局部电荷离域指数. 我们重点研究这三种三芴酮基COF的局部电荷离域与光催化性能之间的构效关系. 在不同三芴酮基COF中, 1,3,5-三(对甲酰基苯基)苯基COF (TeTpb-COF)展现出21.6 mmol g−1h−1的最高析氢速率, 与2,4,6-三(4-醛基苯基-1,3,5-三嗪基COF (TeTt-COF, 0.2 mmol g−1h−1)相比, 光催化析氢性能提高了108倍. 这种性能的增强可归因于其强大的分子内置电场提高了供体-受体嵌段单元中光生电荷的有效分离效率. 这项工作证实了调整构建块可以极大增强三芴酮基COFs中的局部偶极矩, 从而显著改善光催化析氢性能. 构建模块的调控策略为创建高效的新型COF基光催化析氢平台提供了新机会.

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Acknowledgements

Li X thanks the National Natural Science Foundation of China (22378148, 21975084, and 51672089) and the Natural Science Foundation of Guangdong Province (2021A1515010075) for their supports.

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Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Institute of Biomass Engineering, Key Laboratory of Energy Plants Resource and Utilization, Ministry of Agriculture and Rural Affairs, South China Agricultural University, Guangzhou, 510642, China

    Lei Hao  (郝磊), Rongchen Shen  (沈荣晨) & Xin Li  (李鑫)

  2. Henan Key Laboratory of Infrared Materials and Spectrum Measures and Applications, School of Physics, Henan Normal University, Xinxiang, 453007, China

    Chaochao Qin  (秦朝超)

  3. State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan, 430070, China

    Neng Li  (李能)

  4. Key Laboratory of Efficient Utilization of Oil and Gas Resources in Longdong, College of Petroleum and Chemical Engineering, Longdong University, Qingyang, 745000, China

    Haobin Hu  (胡浩斌)

  5. Hubei Key Lab Low Dimens Optoelect Mat & Devices, Hubei University of Arts and Science, Xiangyang, 441053, China

    Guijie Liang  (梁桂杰)

Authors
  1. Lei Hao  (郝磊)
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  2. Rongchen Shen  (沈荣晨)
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  4. Neng Li  (李能)
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  6. Guijie Liang  (梁桂杰)
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  7. Xin Li  (李鑫)
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Contributions

Author contributions Hao L, Shen R and Li X designed the systems, synthesized the photocatalysts, performed the experimental measurement and the computational studies, analyzed the data as well as wrote the manuscript. Qin C and Liang G carried out transient absorption spectroscopy experiments. Hu H helped revise the language of the manuscript. Li N conducted DFT calculations on the hydrogen adsorption free energy of COF-based materials.

Corresponding authors

Correspondence to Guijie Liang  (梁桂杰) or Xin Li  (李鑫).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Supplementary information Experimental details and supporting data are available in the online version of the paper.

Lei Hao is currently pursuing his PhD degree under the supervision of Prof. Xin Li at the College of Materials and Energy, South China Agricultural University. He received his Master’s degree from Tianjin University of Science and Technology in 2020. His current research interests focus on the design and construction of novel COF-based efficient photocatalysts as well as the study of photocatalysis.

Rongchen Shen received his BS and PhD degrees from Huaibei Normal University in 2016 and South China Agricultural University in 2022, respectively. Then, he worked as a postdoctoral researcher at the South China Agricultural University. His research interests include photocatalysis, biomass engineering and the 2D COF materials.

Guijie Liang received his BS and PhD degrees in materials science and engineering from Wuhan Textile University in 2005 and Xi’an Jiaotong University in 2011, respectively. Then, he joined Hubei University of Arts and Science as a faculty staff member, and became a professor in 2020. In 2014–2015, he worked at the Department of Chemistry of Emory University in USA as a postdoctor. In 2017–2018, he worked as a visiting scholar at Dalian Institute of Chemical Physics, Chinese Academy of Sciences. His research interests include ultrafast spectroscopy, exciton dynamics, solar energy conversion and utilization, solar cells and photocatalysis.

Xin Li received his BS and PhD degrees in chemical engineering from Zhengzhou University in 2002 and South China University of Technology in 2007, respectively. Then, he joined the South China Agricultural University as a faculty staff member, and became a professor in 2017. During 2012 and 2019, he worked as a visiting scholar at the Electrochemistry Center, the University of Texas at Austin, and the Department of Chemistry, University of Utah, respectively. His research interests include photocatalysis, photoelectrochemistry, adsorption, biomass engineering and the development of related materials and devices.

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Regulating local polarization in truxenone-based covalent organic frameworks for boosting photocatalytic hydrogen evolution

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Hao, L., Shen, R., Qin, C. et al. Regulating local polarization in truxenone-based covalent organic frameworks for boosting photocatalytic hydrogen evolution. Sci. China Mater. 67, 504–513 (2024). https://doi.org/10.1007/s40843-023-2747-6

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