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Polyoxometalates coupled covalent organic frameworks as highly active photothermal nanoreactor for CO2 cycloaddition

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Abstract

Covalent organic frameworks (COFs)-based nanoreactors have attracted broad interest in many fields due to their void-confinement effects. However, the inherent drawback of conventional nanoreactors is the lack of internal active sites, which limits their widespread utilization. Herein, we report the construction of hierarchical COF (EB-TFP) nanoreactor with pre-synthesized polyoxometalates (POM, [PV2W10O40]5− (PV2W10)) clusters encapsulated inside of COF (POM@COF). PV2W10@EB-TFP anchors nucleophilic-group (Br− ions) and PV2W10 anion cluster within the COF framework via electrostatic interactions, which not only simplifies the reaction system but also enhances catalytic efficiency. The reaction performance of the PV2W10@EB-TFP nanoreactor can be tuned to achieve excellent catalytic activity in CO2 cycloaddition reaction (CCR) for ∼ 97.63% conversion and ∼ 100% selectivity under visible light irradiation. A mechanistic study based on density functional theory (DFT) calculations and in-situ characterization was also carried out. In summary, we have reported a method for achieving the uniform dispersion of POM single clusters into COF nanoreactor, demonstrating the potential of POM@COF nanoreactor for synergistic photothermal catalytic CO2 cycloaddition.

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Acknowledgements

This work is supported by the National Natural Science Foundation of China (No. 22101289), Hundred Talents Programs in Chinese Academy of Sciences, the National Key Research and Development Program of China (No. 2021YFA1502200), Bellwethers Project of Zhejiang Research and Development Plan (No. 2022C01158), Ningbo S&T Innovation 2025 Major Special Program (Nos. 2020Z107 and 2022Z205), and Ningbo Yongjiang Talent Introduction Programme (Nos. 2021A-111-G and 2021A-036-B). We thank the discussion with Dr. Chenxi Guo from SUPCON Technology Co., Ltd. for the DFT computations in this work.

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Authors and Affiliations

  1. School of Environmental Science and Engineering, Shaanxi University of Science and Technology, Xi’an, 710021, China

    Tian Wang, Yunqing Zhu & Junfeng Niu

  2. Key Laboratory of Advanced Fuel Cells and Electrolyzers Technology of Zhejiang Province, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, 315201, China

    Tian Wang, Wei Wang, Zhiyi Lu & Peilei He

  3. College of Environmental Science and Engineering, North China Electric Power University, Beijing, 102206, China

    Junfeng Niu

  4. University of Chinese Academy of Sciences, Beijing, 100049, China

    Zhiyi Lu & Peilei He

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  1. Tian Wang
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Correspondence to Yunqing Zhu or Peilei He.

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Wang, T., Zhu, Y., Wang, W. et al. Polyoxometalates coupled covalent organic frameworks as highly active photothermal nanoreactor for CO2 cycloaddition. Nano Res. (2024). https://doi.org/10.1007/s12274-024-6626-1

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