Surface-exposed silver nanoclusters inside molecular metal oxide cavities

K. Yonesato, D. Yanai, S. Yamazoe, D. Yokogawa, T. Kikuchi, K. Yamaguchi, K. Suzuki

Nat. Chem., DOI: 10.1038/s41557-023-01234-w

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-defned hybrids of metal nanoclusters and metal oxides with exposed surfaces and/or interfaces. Here we report the sequential synthesis of structurally well-defned {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 fndings will serve for the discrete synthesis of surface-exposed metal nanoclusters stabilized by molecular metal oxides, which may in turn fnd applications in, for example, the felds of catalysis and energy conversion.