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Phase engineering of polyoxometalate assembled superstructures

Nature Synthesis volume 3, pages 1039–1048 (2024)Cite this article

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Abstract

Superstructures of cluster assemblies have extraordinary properties compared with individual clusters, however, their precise synthesis and phase engineering remain challenging. Here the modular synthesis of a library of clusters based on anisotropic polyoxometalate clusters (CTA)2(TBA)2[PW11MO39] (PW11M) is reported. Different phases of superstructures including nanoribbons, spiral nanosheets, tetragonal nanosheets, polyhedral frameworks and nanotubes are prepared by the tuning of interactions between and inside the polyoxometalate building blocks. This synthetic strategy can be applied to six kinds of PW11M cluster building block. A phase diagram based on these results, which can be used to adjustably assemble polyoxometalate clusters, is presented. The direct bonding of clusters and electron delocalization among nanoribbons results in improved conductivity and reduced energy barrier for redox reactions. The nanoribbons exhibit enhanced activity for photoresponse and catalytic olefin epoxidation compared with unassembled clusters. The phase engineering of cluster-assembled superstructures with atomic precision models may help understand the structure–property relationship at the sub-nanometre scale.

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Fig. 1: Schematic models of different phases of PW11M superstructures.
Fig. 2: The PW11Nd nanoribbons and spiral nanosheets.
Fig. 3: The PW11Nd tetragonal nanosheets and polyhedral framework.
Fig. 4: Constructions of PW11M superstructures.
Fig. 5: Electronic structure, photoresponse and catalytic performance of PW11Nd superstructures.

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All data that support this work are available within the paper and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Key R&D Program of China (grant no. 2023YFB3507700 to X.W.), NSFC (grant nos. 22241502, 22035004, 22250710677, 22305137) (to X.W.) and the China Postdoctoral Science Foundation (grant nos. 2023M731918 to F.Z. and 2022M721798 to Z.L.).

Author information

Authors and Affiliations

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

    Fenghua Zhang, Haoyang Li, Zhong Li, Qingda Liu & Xun Wang

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  1. Fenghua Zhang
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  2. Haoyang Li
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Contributions

Q.L. and X.W. contributed the idea and provided the guidance. F.Z. performed most of the experiments. Z.L. provided theoretical analysis and supervision. H.L. provided the guidance on ELF and photodetection properties, respectively. X.W. wrote the manuscript with input from all authors.

Corresponding authors

Correspondence to Zhong Li, Qingda Liu or Xun Wang.

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The authors declare no competing interests.

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Nature Synthesis thanks Xun Hong and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alison Stoddart, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Supplementary Methods, Figs. 1–43 and Tables 1–5.

Source data

Source Data Fig. 2

Data of height profile.

Source Data Fig. 3

Data of small-angle XRD.

Source Data Fig. 5

Data of electronic structure, photoresponse and catalytic performance.

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Zhang, F., Li, H., Li, Z. et al. Phase engineering of polyoxometalate assembled superstructures. Nat. Synth 3, 1039–1048 (2024). https://doi.org/10.1038/s44160-024-00569-7

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