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Self-assembly of polyoxometalate clusters into two-dimensional clusterphene structures featuring hexagonal pores

Nature Chemistry volume 14, pages 433–440 (2022)Cite this article

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Abstract

Two-dimensional (2D) structures have been shown to possess interesting and potentially useful properties. Because of their isotropic structure, however, clusters tend to assemble into 3D architectures. Here we report the assembly of polyoxometalate clusters into layered structures that feature uniform hexagonal pores and in-plane electron delocalization properties. Because these structures are 2D and visually reminiscent of graphene, they are referred to as ‘clusterphenes’. A series of multilayer and monolayer clusterphenes have been constructed with 13 types of polyoxometalate cluster. The resulting clusterphenes were shown to exhibit substantially improved stability and catalytic efficiency towards olefin epoxidation reactions, with a turnover frequency of 4.16 h−1, which is 76.5 times that of the unassembled clusters. The catalytic activity of the clusterphenes derives from the electron delocalization between identical clusters within the 2D layer, which efficiently reduces the activation energy of the catalytic reaction.

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Fig. 1: Schematics and MD simulations of the clusterphene constructions.
Fig. 2: The NdPW11 monolayer clusterphenes.
Fig. 3: Characterizations of NdPW11 multilayer clusterphenes and ultrathin nanobelts.
Fig. 4: TEM images of MPW11 monolayer clusterphenes.
Fig. 5: Epoxidation of olefins with H2O2 catalysed by the NdPW11 clusterphene.
Fig. 6: Molecular models and activation energies of NdPW11 building blocks for redox reactions.

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All the data supporting the findings of this study are available within the article and its Supplementary Information and also from the corresponding authors upon reasonable request.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2017YFA0700101), NSFC (22035004), the XPLORER PRIZE, the China National Postdoctoral Program for Innovative Talents (BX2021145) and Shuimu Tsinghua Scholar Program. We thank X. Xu for his help with density functional theory calculations.

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Authors and Affiliations

  1. Key Lab of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing, China

    Qingda Liu, Hanshi Hu, Jing Zhuang & Xun Wang

  2. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, China

    Qinghua Zhang

  3. School of Materials Science and Engineering, State Key Laboratory of Separation Membranes and Membrane Processes, Tiangong University, Tianjin, China

    Wenxiong Shi

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  1. Qingda Liu
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Contributions

X.W. proposed and guided the project. Q.L. designed, planned and carried out the experiments and analysed data. Q.Z. performed the TEM imaging and analysis. W.S. performed the MD simulations. H.H. performed the density functional theory calculations. J.Z. performed the gas chromatography mass spectrometry tests. All authors discussed the results and commented on the manuscript.

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Correspondence to Xun Wang.

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Nature Chemistry thanks Panchao Yin and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Methods, Figs. 1–25, Tables 1–9 and references.

Supplementary Data 1

Configurations of assemblies before and after MD simulations.

Supplementary Data 2

Atomic coordinates of POM cluster calculated by DFT.

Supplementary Data 3

Source data for Supplementary Figs. 15 and 16.

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Liu, Q., Zhang, Q., Shi, W. et al. Self-assembly of polyoxometalate clusters into two-dimensional clusterphene structures featuring hexagonal pores. Nat. Chem. 14, 433–440 (2022). https://doi.org/10.1038/s41557-022-00889-1

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