Modulating the structures of subnanometric metal clusters at the atomic level is a great synthetic and characterization challenge in catalysis. Here, we show how the catalytic properties of subnanometric platinum clusters (0.5–0.6 nm) confined in the sinusoidal 10R channels of purely siliceous MFI zeolite are modulated upon introduction of partially reduced tin species that interact with the noble metal at the metal/support interface. The platinum–tin clusters are stable in H₂ over an extended period of time (>6 h), even at high temperatures (for example, 600 °C), which is determined by only a few additional tin atoms added to the platinum clusters. The structural features of platinum–tin clusters, which are not immediately visible by conventional characterization techniques but can be established after combination of in situ extended X-ray absorption fine structure, high-angle annular dark-field scanning transmission electron microscopy and CO infrared data, are key to providing a one-order of magnitude lower deactivation rate in the propane dehydrogenation reaction while maintaining high intrinsic (initial) catalytic activity.

在原子水平上调节亚纳米金属团簇的结构是催化中巨大的合成和表征挑战。在这里，我们展示了如何限制局限在纯硅质MFI沸石正弦曲线10R通道中的亚纳米级铂簇（0.5–0.6 nm）的催化性能在引入部分还原的锡物种后与金属/载体界面相互作用，从而与贵金属相互作用。铂锡簇在H ₂中稳定即使在高温下（例如600°C），也要经过较长时间（> 6小时），这取决于添加到铂簇中的锡原子数。铂-锡团簇的结构特征不能通过常规表征技术立即看到，但可以在原位扩展的X射线吸收精细结构，高角度环形暗场扫描透射电子显微镜和CO红外数据结合后确定在保持高的固有（初始）催化活性的同时，对于在丙烷脱氢反应中提供低一个数量级的失活速率是关键。