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Phase engineering of polyoxometalate assembled superstructures

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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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Data availability

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

References

  1. Khanna, S. N. & Jena, P. Atomic clusters: building blocks for a class of solids. Phys. Rev. B 51, 13705–13716 (1995).

    CAS  Google Scholar 

  2. Ritchie, C. et al. Spontaneous assembly and real-time growth of micrometre-scale tubular structures from polyoxometalate-based inorganic solids. Nat. Chem. 1, 47–52 (2009).

    CAS  PubMed  Google Scholar 

  3. Fernández, J. A. et al. Polyoxometalates with internal cavities: Redox activity, basicity, and cation encapsulation in [Xn+P5W30O110](15-n)− preyssler complexes, with X = Na+, Ca2+, Y3+, La3+, Ce3+, and Th4+. J. Am. Chem. Soc. 129, 12244–12253 (2007).

    PubMed  Google Scholar 

  4. Misra, A., Kozma, K., Streb, C. & Nyman, M. Beyond charge balance: counter-cations in polyoxometalate chemistry. Angew. Chem. Int. Ed. 59, 596–612 (2020).

    CAS  Google Scholar 

  5. Franco-Castillo, I. et al. Polyoxometalate-ionic liquids (POM-ILs) as anticorrosion and antibacterial coatings for natural stones. Angew. Chem. Int. Ed. 57, 14926–14931 (2021).

    Google Scholar 

  6. Lin, C. G., Hu, J. & Song, Y. F. Polyoxometalate-functionalized nanocarbon materials for energy conversion, energy storage, and sensor systems. Adv. Inorg. Chem. 69, 181–212 (2017).

    CAS  Google Scholar 

  7. Moussawi, M. A. et al. Polyoxometalate, cationic cluster, and γ-cyclodextrin: from primary interactions to supramolecular hybrid materials. J. Am. Chem. Soc. 139, 12793–12803 (2017).

    CAS  PubMed  Google Scholar 

  8. Li, Y. et al. Double-helical assembly of heterodimeric nanoclusters into supercrystals. Nature 594, 380–384 (2021).

    CAS  PubMed  Google Scholar 

  9. Hu, B. et al. Single-crystal superstructures via hierarchical assemblies of giant rubik’s cubes as tertiary building units. Angew. Chem. Int. Ed. 62, e202219025 (2023).

    CAS  Google Scholar 

  10. Hou, L. et al. Synthesis of a monolayer fullerene network. Nature 606, 507–510 (2022).

    CAS  PubMed  Google Scholar 

  11. Li, W. & Sun, M. Electronic band structure and anisotropic optical properties of bulk and monolayer fullerene networks. Spectrochim Acta A. 298, 122756 (2023).

    CAS  Google Scholar 

  12. Peng, B. Monolayer fullerene networks as photocatalysts for overall water splitting. J. Am. Chem. Soc. 144, 19921–19931 (2022).

    CAS  PubMed  PubMed Central  Google Scholar 

  13. Yao, Q. et al. Supercrystal engineering of atomically precise gold nanoparticles promoted by surface dynamics. Nat. Chem. 15, 230–239 (2023).

    CAS  PubMed  Google Scholar 

  14. Higaki, T. et al. Atomically tailored gold nanoclusters for catalytic application. Angew. Chem. Int. Ed. 58, 8291–8302 (2019).

    CAS  Google Scholar 

  15. Jin, R. Quantum sized, thiolate-protected gold nanoclusters. Nanoscale 2, 343–362 (2010).

    CAS  PubMed  Google Scholar 

  16. Liu, Q. & Wang, X. Fabricating sub-nanometer materials through cluster assembly. Chem. Sci. 13, 12280–12289 (2022).

    CAS  PubMed  PubMed Central  Google Scholar 

  17. Li, Z., Liu, Q. & Wang, X. Two-dimensional cluster-assembled materials with properties beyond their individualities and bulks. Matter 6, 3747–3762 (2023).

    CAS  Google Scholar 

  18. Nyman, M., Rahman, T. & Colliard, I. Decaniobate: the fruit fly of niobium polyoxometalate chemistry. Acc. Chem. Res. 56, 3616–3625 (2023).

    CAS  PubMed  Google Scholar 

  19. Maksimchuk, N. V. et al. Relevance of protons in heterolytic activation of H2O2 over Nb(V): insights from model studies on Nb-substituted polyoxometalates. ACS Catal. 8, 9722–9737 (2018).

    CAS  Google Scholar 

  20. Liu, R. & Streb, C. Polyoxometalate-single atom catalysts (POM-SACs) in energy research and catalysis. Adv. Energy Mater. 11, 2101120 (2021).

    CAS  Google Scholar 

  21. Long, D. L., Burkholder, E. & Cronin, L. Polyoxometalate clusters, nanostructures and materials: from self assembly to designer materials and devices. Chem. Soc. Rev. 36, 105–121 (2007).

    CAS  PubMed  Google Scholar 

  22. Li, X. et al. A polymeric co-assembly of subunit vaccine with polyoxometalates induces enhanced immune responses. Nano Res. 15, 4175–4180 (2022).

    CAS  PubMed  Google Scholar 

  23. Putaj, P. & Lefebvre, F. Polyoxometalates containing late transition and noble metal atoms. Coord. Chem. Rev. 255, 1642–1685 (2011).

    CAS  Google Scholar 

  24. Anyushin, A. V., Kondinski, A. & Parac-Vogt, T. N. Hybrid polyoxometalates as post-functionalization platforms: From fundamentals to emerging applications. Chem. Soc. Rev. 49, 382–432 (2020).

    CAS  PubMed  Google Scholar 

  25. Li, H., Zheng, L., Lu, Q., Li, Z. & Wang, X. A monolayer crystalline covalent network of polyoxometalate clusters. Sci. Adv. 9, eadi6595 (2023).

    CAS  PubMed  PubMed Central  Google Scholar 

  26. Liu, Q. et al. Self-assembly of polyoxometalate clusters into two-dimensional clusterphene structures featuring hexagonal pores. Nat. Chem. 14, 433–440 (2022).

    PubMed  Google Scholar 

  27. Li, Z., Zhang, Z., Hu, H., Liu, Q. & Wang, X. Synthesis of two-dimensional polyoxoniobate-based clusterphenes with in-plane electron delocalization. Nat. Synth. 2, 989–997 (2023).

    Google Scholar 

  28. Li, Z. et al. Single-walled cluster nanotubes for single-atom catalysts with precise structures. J. Am. Chem. Soc. 146, 450–459 (2024).

    CAS  PubMed  Google Scholar 

  29. He, P., Xu, B., Wang, P., Liu, H. & Wang, X. A monolayer polyoxometalate superlattice. Adv. Mater. 26, 4339–4344 (2014).

    CAS  PubMed  Google Scholar 

  30. Nie, S., Wu, L. & Wang, X. Electron-delocalization-stabilized photoelectrocatalytic coupling of methane by NiO-polyoxometalate sub-1 nm heterostructures. J. Am. Chem. Soc. 145, 23681–23690 (2023).

    CAS  PubMed  Google Scholar 

  31. Liu, J. et al. Incorporation of clusters within inorganic materials through their addition during nucleation steps. Nat. Chem. 11, 839–845 (2019).

    CAS  PubMed  Google Scholar 

  32. Shearer, M. J. et al. Complex and noncentrosymmetric stacking of layered metal dichalcogenide materials created by screw dislocations. J. Am. Chem. Soc. 139, 3496–3504 (2017).

    CAS  PubMed  Google Scholar 

  33. Zhang, L. M. et al. Three-dimensional spirals of atomic layered MoS2. Nano Lett. 14, 6418–6423 (2014).

    CAS  PubMed  Google Scholar 

  34. Sarma, P. V., Patil, P. D., Barman, P. K., Kini, R. N. & Shaijumon, M. M. Controllable growth of few-layer spiral WS2. RSC Adv. 6, 376–382 (2016).

    CAS  Google Scholar 

  35. Ly, T. H. et al. Vertically conductive MoS2 spiral pyramid. Adv. Mater. 28, 7723–7728 (2016).

    CAS  PubMed  Google Scholar 

  36. Zhuang, A. et al. Screw‐dislocation-driven bidirectional spiral growth of Bi2Se3 nanoplates. Angew. Chem. Int. Ed. 53, 6425–6429 (2014).

    CAS  Google Scholar 

  37. Forticaux, A., Dang, L. N., Liang, H. F. & Jin, S. Controlled synthesis of layered double hydroxide nanoplates driven by screw dislocations. Nano Lett. 15, 3403–3409 (2015).

    CAS  PubMed  Google Scholar 

  38. Hu, H. et al. Spiral square nanosheets assembled from Ru clusters. J. Am. Chem. Soc. 145, 12148–12154 (2023).

    CAS  PubMed  Google Scholar 

  39. López, X., Carbó, J. J., Bo, C. & Poblet, J. M. Structure, properties and reactivity of polyoxometalates: a theoretical perspective. Chem. Soc. Rev. 41, 7537–7571 (2012).

    PubMed  Google Scholar 

  40. Gumerova, N. I. & Rompel, A. Synthesis, structures and applications of electron-rich polyoxometalates. Nat. Rev. Chem. 2, 0112 (2018).

    CAS  Google Scholar 

  41. Becke, A. D. & Edgecombe, K. E. A simple measure of electron localization in atomic and molecular systems. J. Chem. Phys. 92, 5397–5403 (1990).

    CAS  Google Scholar 

  42. Silvi, B. & Savin, A. Classification of chemical bonds based on topological analysis of electron localization functions. Nature 371, 683–686 (1994).

    CAS  Google Scholar 

  43. Liu, L., Li, P., Yuan, L. F., Cheng, L. & Yang, J. From isosuperatoms to isosupermolecules: new concepts in cluster science. Nanoscale 8, 12787–12792 (2016).

    CAS  PubMed  Google Scholar 

  44. Liu, Q. & Wang, X. Sub-nanometric materials: electron transfer, delocalization, and beyond. Chem. Catal. 2, 1257–1266 (2022).

    CAS  Google Scholar 

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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.).

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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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  3. Zhong Li
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  4. Qingda Liu
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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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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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