Materials Science Division, Argonne National Lab, 9700 S Cass Ave., Argonne, IL 60439, USA.
Nanophotonics Center, Korea Institute of Science and Technology, Seoul, 02792, South Korea.
Angew Chem Int Ed Engl. 2018 Jan 22;57(4):909-913. doi: 10.1002/anie.201708092. Epub 2018 Jan 2.
Single atoms and few-atom clusters of platinum are uniformly installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 °C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and X-ray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support.
通过靶向气相合成，将铂的单原子和少原子团簇均匀地安装在金属有机骨架（MOF）NU-1000 的氧化锆节点上。被有机配体位隔离的催化 Pt 团簇表现出对乙烯加氢的高催化活性，同时在高达 200°C 的温度下表现出抗烧结性。原位红外光谱揭示了存在单原子和少原子团簇，这取决于合成条件。在位 X 射线吸收光谱和 X 射线配对分布分析揭示了在流态下化学结合环境和团簇尺寸稳定性的独特变化。密度泛函理论计算阐明了新型催化剂上乙烯加氢的有利反应途径。这些结果表明，MOF 中的原子层沉积（ALD）是在高表面积载体上合理合成尺寸选择的团簇（包括贵金属）的通用方法。
