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Surface-exposed silver nanoclusters inside molecular metal oxide cavities

Nature Chemistry volume 15, pages 940–947 (2023)Cite this article

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Abstract

The surfaces of metal nanoclusters, including their interface with metal oxides, exhibit a high reactivity that is attractive for practical purposes. This high reactivity, however, has also hindered the synthesis of structurally well-defined hybrids of metal nanoclusters and metal oxides with exposed surfaces and/or interfaces. Here we report the sequential synthesis of structurally well-defined {Ag30} nanoclusters in the cavity of ring-shaped molecular metal oxides known as polyoxometalates. The {Ag30} nanoclusters possess exposed silver surfaces yet are stabilized both in solution and the solid state by the surrounding ring-shaped polyoxometalate species. The clusters underwent a redox-induced structural transformation without undesirable agglomeration or decomposition. Furthermore, {Ag30} nanoclusters showed high catalytic activity for the selective reduction of several organic functional groups using H2 under mild reaction conditions. We believe that these findings will serve for the discrete synthesis of surface-exposed metal nanoclusters stabilized by molecular metal oxides, which may in turn find applications in, for example, the fields of catalysis and energy conversion.

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Fig. 1: Schematic representation of the synthesis of silver nanoclusters possessing exposed surfaces and interfaces with metal oxide cavities.
Fig. 2: Molecular structures and electronic states of {Ag16}16+ and {Ag30}22+ nanoclusters within ring-shaped POM cavities (Ag16 and Ag30).
Fig. 3: Molecular structure and electronic state of {Ag30}16+ nanocluster within the ring-shaped POM cavity (Ag30′).
Fig. 4: Structure transformation and catalytic application of {Ag30} nanocluster using H2.

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Data availability

Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2103710 (Ag16), 2103711 (Ag30) and 2103712 (Ag30′). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. All other spectroscopic and crystallographic data are included in the Supplementary Information. Source data are provided with this paper.

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Acknowledgements

We gratefully acknowledge the financial support from JST PRESTO (JPMJPR18T7, JPMJPR19T9), JST FOREST (JPMJFR213M), JSPS KAKENHI (20H02749, 20H04659), and the JSPS Core-to-Core program, the Noguchi Institute and the Toray Science Foundation. Some of the computations were performed using the Research Center for Computational Science, Okazaki, Japan. XAFS measurements at SPring-8 were conducted with the approval of the Japan Synchrotron Radiation Research Institute (proposal numbers 2020A1219, 2021A1272, 2022A1627). Single-crystal X-ray diffraction measurements at SPring-8 were conducted with the approval of the Japan Synchrotron Radiation Research Institute (proposal numbers 2021A1034, 2022A1111, 2022B1605). We thank S. Kikkawa (Tokyo Metropolitan University) for help with XAFS measurements at SPring-8. We thank T. Kojima (Osaka University) for help with single-crystal X-ray diffraction measurements at SPring-8.

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Authors and Affiliations

  1. Department of Applied Chemistry, School of Engineering, The University of Tokyo, Tokyo, Japan

    Kentaro Yonesato, Daiki Yanai, Kazuya Yamaguchi & Kosuke Suzuki

  2. Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, Tokyo, Japan

    Seiji Yamazoe

  3. Precursory Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST), Kawaguchi, Japan

    Seiji Yamazoe & Kosuke Suzuki

  4. Graduate School of Arts and Science, The University of Tokyo, Tokyo, Japan

    Daisuke Yokogawa

  5. Rigaku Corporation, Tokyo, Japan

    Takashi Kikuchi

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  1. Kentaro Yonesato
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Contributions

K.S. conceived and designed the project. K.S. and K.Ya supervised the project. K.Yo. performed the major parts of synthesis and characterization of compounds. K.Yo. and T.K. performed crystallographic analysis. S.Y., K.Yo. and K.S. performed XAFS studies. D.Yo. and K.S. performed DFT studies. D.Ya. and K.S. performed catalytic studies.

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Correspondence to Kazuya Yamaguchi or Kosuke Suzuki.

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Nature Chemistry thanks Lei Zhang 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 Tables 1–10, Figs. 1–26 and Notes 1–5.

Supplementary Data 1

Crystallographic data of Ag16.

Supplementary Data 2

Crystallographic data of Ag30.

Supplementary Data 3

Crystallographic data of Ag30′.

Supplementary Data 4

Source data for Supplementary Figs. 8 and 17, titration experiments.

Source data

Source Data Fig. 2

Observed and fitting data for XPS.

Source Data Fig. 3

Observed and fitting data for XPS.

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Yonesato, K., Yanai, D., Yamazoe, S. et al. Surface-exposed silver nanoclusters inside molecular metal oxide cavities. Nat. Chem. 15, 940–947 (2023). https://doi.org/10.1038/s41557-023-01234-w

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