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Selective scandium ion capture through coordination templating in a covalent organic framework

Nature Chemistry volume 15, pages 1599–1606 (2023)Cite this article

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Abstract

The use of coordination complexes within covalent organic frameworks can significantly diversify the structures and properties of this class of materials. Here we combined coordination chemistry and reticular chemistry by preparing frameworks that consist of a ditopic (p-phenylenediamine) and mixed tritopic moieties—an organic ligand and a scandium coordination complex of similar sizes and geometries, both bearing terminal phenylamine groups. Changing the ratio of organic ligand to scandium complex enabled the preparation of a series of crystalline covalent organic frameworks with tunable levels of scandium incorporation. Removal of scandium from the material with the highest metal content subsequently resulted in a ‘metal-imprinted’ covalent organic framework that exhibits a high affinity and capacity for Sc3+ ions in acidic environments and in the presence of competing metal ions. In particular, the selectivity of this framework for Sc3+ over common impurity ions such as La3+ and Fe3+ surpasses that of existing scandium adsorbents.

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Fig. 1: Design strategy and synthesis of the Sc–COFs and MICOFs.
Fig. 2: Characterization of Sc–COF-33.
Fig. 3: Scandium(III) uptake in MICOF-33.
Fig. 4: Scandium(III) uptake selectivity.

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Data availability

The authors declare that the main data supporting the findings of this study can be accessed at https://doi.org/10.6084/m9.figshare.19602262 (ref. 45). Source data are provided with this paper.

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Acknowledgements

G.Z. was supported by the National Key R&D Program of China (grant no. 2022YFB3805902), the National Natural Science Foundation of China (grant nos 22131004 and U21A20330) and the ‘111’ project (grant no. B18012). Y. Yang was supported by the National Natural Science Foundation of China (grant no. 52204389). Y. Yuan was supported by the National Natural Science Foundation of China (grant no. 21975039) and the Fundamental Research Funds for the Central Universities, Excellent Youth Team Program (grant no. 2412023YQ001). K.R.M. and J.R.L. were supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under award DE-SC0019992.

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Author notes

  1. These authors contributed equally: Ye Yuan, Yajie Yang.

Authors and Affiliations

  1. Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun, China

    Ye Yuan, Yajie Yang & Guangshan Zhu

  2. Department of Chemistry, University of California, Berkeley, CA, USA

    Katie R. Meihaus & Jeffrey R. Long

  3. Pritzker School of Molecular Engineering, University of Chicago, Chicago, IL, USA

    Shenli Zhang

  4. Key Laboratory of Automobile Materials MOE, and School of Materials Science & Engineering, and Electron Microscopy Center, and Jilin Provincial International Cooperation Key Laboratory of High-Efficiency Clean Energy Materials, Jilin University, Changchun, China

    Xin Ge & Wei Zhang

  5. Department of Chemical Engineering, University of California, Davis, CA, USA

    Roland Faller

  6. Department of Chemical & Biomolecular Engineering, University of California, Berkeley, CA, USA

    Jeffrey R. Long

  7. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Jeffrey R. Long

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Contributions

Y. Yang carried out the experiments, performed the data interpretation and draughted the initial manuscript. X.G. and W.Z. collected and analysed the TEM and STEM data. J.R.L. and K.R.M. helped design the experiments and wrote portions of the manuscript. S.Z. and R.F. performed the theoretical calculations. Y. Yuan and G.Z. developed the concept, supervised the experiments and draughted the manuscript.

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Correspondence to Jeffrey R. Long or Guangshan Zhu.

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Nature Chemistry thanks Shengqian Ma, Dan Zhao and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Yuan, Y., Yang, Y., Meihaus, K.R. et al. Selective scandium ion capture through coordination templating in a covalent organic framework. Nat. Chem. 15, 1599–1606 (2023). https://doi.org/10.1038/s41557-023-01273-3

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