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Post-synthetic metalation of organic cage for enhanced porosity and catalytic performance

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Abstract

Porous organic cages (POCs) have shown great potential in many applications, and post-synthetic modification (PSM) has been confirmed to be an effective strategy to tailor their structures and related functionalities. However, it is extremely challenging to develop a general platform for simple-to-make functional POCs for advanced applications by PSM method. Herein, we reported that octahedral calix[4]resorcinarene-based hydrazone-linked porous organic cage (HPOC-401) provides an excellent platform for post-synthetic metalation by various transition metal (TM) ions under mild conditions due to the abundance of coordination sites in its skeleton. Such metalated products (HPOC-401-TM) exhibit Brunauer-Emmett-Teller (BET) surface area up to 1,456 m2 g−1, much higher than that of the pristine HPOC-401, which has a BET value of 474 m2 g−1. Moreover, the metalation and porosity increases further influence their gas capture, separation, as well as catalytic performance. For instance, HPOC-401-TM products exhibit higher CO2, H2, and C2 hydrocarbon gas uptake, as well as higher C2H6/C2H4 selectivity than HPOC-401. Moreover, the HPOC-401-TM also shows better catalytic performance in the cycloaddition of CO2 with epoxides compared to HPOC-401. These findings uncover a simple yet effective approach for modifying the porosity characteristics of organic cages, which will undoubtedly expand their future implementations.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22071244), the Youth Innovation Promotion Association CAS (2022305), the Natural Science Foundation of Fujian Province of China (2022J01503, 2020J05087) and the China Postdoctoral Science Foundation (2020M671954).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. State Key Lab of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China

    Miao Yang, Xun Chen, Yifei Xie, El-Sayed M. El-Sayed, Ning Xu, Wenjing Wang, Kongzhao Su & Daqiang Yuan

  2. University of the Chinese Academy of Sciences, Beijing, 100049, China

    Yifei Xie, El-Sayed M. El-Sayed, Kongzhao Su & Daqiang Yuan

  3. College of Chemistry, Fuzhou University, Fuzhou, 310116, China

    Xun Chen

  4. Chemical Refining Laboratory, Refining Department, Egyptian Petroleum Research Institute, Nasr City, 11727, Egypt

    El-Sayed M. El-Sayed

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  1. Miao Yang
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Correspondence to Kongzhao Su or Daqiang Yuan.

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Supporting information The supporting information is available online at https://chem.scichina.com and https://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Yang, M., Chen, X., Xie, Y. et al. Post-synthetic metalation of organic cage for enhanced porosity and catalytic performance. Sci. China Chem. 66, 1763–1770 (2023). https://doi.org/10.1007/s11426-022-1562-8

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