Imaoka Takane, Akanuma Yuki, Haruta Naoki, Tsuchiya Shogo, Ishihara Kentaro, Okayasu Takeshi, Chun Wang-Jae, Takahashi Masaki, Yamamoto Kimihisa
Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, Yokohama, 226-8503, Japan.
ERATO-JST, Saitama, Kawaguchi, 332-0012, Japan.
Nat Commun. 2017 Sep 25;8(1):688. doi: 10.1038/s41467-017-00800-4.
Subnanometer noble metal clusters have enormous potential, mainly for catalytic applications. Because a difference of only one atom may cause significant changes in their reactivity, a preparation method with atomic-level precision is essential. Although such a precision with enough scalability has been achieved by gas-phase synthesis, large-scale preparation is still at the frontier, hampering practical applications. We now show the atom-precise and fully scalable synthesis of platinum clusters on a milligram scale from tiara-like platinum complexes with various ring numbers (n = 5-13). Low-temperature calcination of the complexes on a carbon support under hydrogen stream affords monodispersed platinum clusters, whose atomicity is equivalent to that of the precursor complex. One of the clusters (Pt) exhibits high catalytic activity in the hydrogenation of styrene compared to that of the other clusters. This method opens an avenue for the application of these clusters to preparative-scale catalysis.The catalytic activity of a noble metal nanocluster is tied to its atomicity. Here, the authors report an atom-precise, fully scalable synthesis of platinum clusters from molecular ring precursors, and show that a variation of only one atom can dramatically change a cluster's reactivity.
亚纳米级贵金属簇具有巨大潜力，主要用于催化应用。由于仅一个原子的差异就可能导致其反应活性发生显著变化，因此具有原子级精度的制备方法至关重要。尽管气相合成已实现了具有足够可扩展性的这种精度，但大规模制备仍处于前沿阶段，阻碍了实际应用。我们现在展示了从具有不同环数（n = 5 - 13）的冠状铂配合物以毫克规模实现原子精确且完全可扩展的铂簇合成。在氢气流下将配合物在碳载体上进行低温煅烧可得到单分散的铂簇，其原子数与前体配合物相当。其中一种簇（Pt）在苯乙烯氢化反应中比其他簇表现出更高的催化活性。该方法为这些簇应用于制备规模的催化开辟了一条途径。贵金属纳米簇的催化活性与其原子数相关。在此，作者报道了从分子环状前体实现原子精确、完全可扩展的铂簇合成，并表明仅一个原子的变化就能显著改变簇的反应活性。
