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Modular assembly of polyoxometalate clusters at the sub-1 nm scale

Nature Protocols (2025)Cite this article

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Abstract

Atomic-level manufacturing enables the bottom-up fabrication of nanomaterials with tailored structures and properties. Clusters with atomic precise structures can be used as superatom building blocks to construct superstructures with exceptional properties beyond their individual properties. However, the programmable and large-scale synthesis of cluster assemblies remains challenging. This protocol describes the detailed experimental procedures for the modular assembly of polyoxometalate (POM) clusters into subnanomaterials by programmable interactions under simple and mild conditions. In this approach different types of POM clusters (0.7–1.8 nm in size) are coated with quaternary ammonium or oleylamine ligands using either two-phase or solvothermal methods. The assembly process depends on the interactions between atom clusters, ligands and the reaction matrix, all of which can be modified to generate a library of subnanometer superstructures. The four intercluster connection modes are metal cation-induced coordinative connection, anion bridged covalent connection, synergistic noncovalent interaction and cluster–nucleus co-assembly. A library that includes single-cluster nanowires, clusterphenes and nanosheets with single-cluster thicknesses, can be prepared within 3–12 h. Owing to their ultrahigh surface atom ratio and electron delocalization, the resulting subnanometer POM assemblies with rich structural and compositional diversity exhibit excellent properties and application potential in terms of mechanics, catalysis and chirality. This procedure is suitable for users with prior expertise in the synthesis of inorganic and cluster-based nanomaterials.

Key points

  • This protocol describes a general synthetic strategy for the modular assembly of polyoxometalate (POM) clusters to construct subnanomaterials.

  • This strategy provides rich structural and compositional diversity for the design of POM-based nanomaterials with programmable connection modes and advanced properties not seen in free POMs or crystals.

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Fig. 1: Modular assembly of POM clusters by programmable interactions.
Fig. 2: Schematic diagrams of the experimental device used for the synthesis of POM-based nanomaterials.
Fig. 3: Structure and characterization of PCAMs with metal cation induced coordinative connections.
Fig. 4: Tetragonal phase structure and characterization of 2D CN–PTA sheets with anion bridged covalent connection.
Fig. 5: Morphology and characterization of the nanotube and nanosheet with synergistic noncovalent interaction.
Fig. 6: PCAMs with cluster–nucleus co-assembly.
Fig. 7: Detailed characterization, simulations and geometry optimization of PCAMs.
Fig. 8: Gelation and adhesion properties of SNW-based organogels and SNWs.
Fig. 9: Catalysis for energy conversion of PCAMs.
Fig. 10: CPL photodetection and CISS characterization of chiral assemblies.

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Data availability

All data supporting the findings of this study are included in the article and the references listed in the Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This work was supported by NSFC (grant nos. 92461314, 22241502, 22035004, 22250710677, 22305137).

Author information

Authors and Affiliations

  1. Engineering Research Center of Advanced Rare Earth Materials, Department of Chemistry, Tsinghua University, Beijing, China

    Fenghua Zhang, Qingda Liu & Xun Wang

  2. Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, China

    Wenxiong Shi

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  1. Fenghua Zhang
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  2. Wenxiong Shi
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  3. Qingda Liu
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Contributions

Q.L. and X.W. conceived and designed the experiments. F.Z. performed the experiments. Q.L. assisted the experiments. F.Z., Q.L. and X.W. drafted the manuscript and developed the protocol. All of the authors discussed the experiments and co-wrote the manuscript.

Corresponding authors

Correspondence to Qingda Liu or Xun Wang.

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The authors declare no competing interests.

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Nature Protocols thanks Haralampos N. Miras and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Key references

Zhang, S. et al. Science 377, 100–104 (2022): https://doi.org/10.1126/science.abm7574

Liu, Q. et al. Nat. Chem. 14, 433–440 (2022): https://doi.org/10.1038/s41557-022-00889-1

Liu, J. et al. Nat. Chem. 11, 839–845 (2019): https://doi.org/10.1038/s41557-019-0303-0

Li, Z. et al. Nat. Synth. 2, 989–997 (2023): https://doi.org/10.1038/s44160-023-00305-7

Zhang, F. et al. Nat. Synth. 3, 1039–1048 (2024): https://doi.org/10.1038/s44160-024-00569-7

Li, H. et al. Sci. Adv. 9, eadi6595 (2023): https://doi.org/10.1126/sciadv.adi6595

Supplementary information

Supplementary Information

Supplementary Methods, and Table 1.

Reporting Summary

Source data

Source Data Tables 1 and 2

Detailed information about the synthesis of various NdPW11 nanosheets. Detailed information about the semi-hydrogenation reaction.

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Zhang, F., Shi, W., Liu, Q. et al. Modular assembly of polyoxometalate clusters at the sub-1 nm scale. Nat Protoc (2025). https://doi.org/10.1038/s41596-025-01212-1

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