From molecular complexes to complex metallic nanostructures--2H solid-state NMR studies of ruthenium-containing hydrogenation catalysts.
From molecular complexes to complex metallic nanostructures--2H solid-state NMR studies of ruthenium-containing hydrogenation catalysts.
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DOI：
10.1002/cphc.201300200
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发表时间：
2013-09
期刊：
影响因子：
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通讯作者：
T. Gutmann;I. del Rosal;B. Chaudret;R. Poteau;H. Limbach;G. Buntkowsky
中科院分区：
文献类型：
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作者：
T. Gutmann;I. del Rosal;B. Chaudret;R. Poteau;H. Limbach;G. Buntkowsky
在过去的几年里，(2)氢固体核磁共振技术与量子化学计算的结合已经发展成为表征非均相催化剂表面氢状态的强大光谱工具。本文对氢在分子络合物、团簇和纳米颗粒体系中的结构和动力学进行了综述，旨在了解氢在加氢催化剂表面的反应机理。采用可变温度(2)H静态和魔角自旋（MAS）固态核磁共振相结合的方法分析了氘/氢的表面态，其中氘的主导四极性相互作用提供了氘/氢在分子物种上的结合情况和局部对称性的信息。利用分子络合物和簇的相关数据库，证明了区分末端Ru-D、桥接Ru2-D、三倍Ru3-D和间隙Ru6-D的可能性。将这些结果与量子化学密度泛函理论（DFT）计算相结合，可以解释复杂“现实世界”纳米结构的(2)H固态数据，从而在分子水平上对反应途径产生新的见解。
In the last years, the combination of (2)H solid-state NMR techniques with quantum-chemical calculations has evolved into a powerful spectroscopic tool for the characterization of the state of hydrogen on the surfaces of heterogeneous catalysts. In the present minireview, a brief summary of this development is given, in which investigations of the structure and dynamics of hydrogen in molecular complexes, clusters and nanoparticle systems are presented, aimed to understand the reaction mechanisms on the surface of hydrogenation catalysts. The surface state of deuterium/hydrogen is analyzed employing a combination of variable-temperature (2)H static and magic-angle spinning (MAS) solid-state NMR techniques, in which the dominant quadrupolar interactions of deuterium give information on the binding situation and local symmetry of deuterium/hydrogen on molecular species. Using a correlation database from molecular complexes and clusters, the possibility to distinguish between terminal Ru-D, bridged Ru2-D, three-fold Ru3-D, and interstitial Ru6-D is demonstrated. Combining these results with quantum-chemical density functional theory (DFT) calculations allows the interpretation of (2)H solid-state data of complex "real world" nanostructures, which yielded new insights into reaction pathways at the molecular level.