Bakker Joost M, Mafuné Fumitaka
Radboud University, Institute for Molecules and Materials, FELIX Laboratory, Toernooiveld 7, 6525 ED Nijmegen, The Netherlands.
Department of Basic Science, School of Arts and Sciences, The University of Tokyo, Komaba, Meguro, Tokyo 153-8902, Japan.
Phys Chem Chem Phys. 2022 Mar 30;24(13):7595-7610. doi: 10.1039/d1cp05760j.
The study of reactions relevant to heterogeneous catalysis on the surface of well-defined metal clusters with full control over the number of consituent atoms and elemental composition can lead to a detailed insight into the interactions between metal and reactants. We here review experimental and theoretical studies involving the adsorption of NO molecules on mostly rhodium-based clusters under near-thermal conditions in a molecular beam. We show how IR spectrosopic characterization can give information on the binding nature of NO to the clusters for at least the first three NO molecules. The complementary technique of thermal desorption spectrometry reveals at what temperatures multiple NO molecules on the cluster surface desorb or combine to form rhodium oxides followed by N elimination. Variation of the cluster elemental composition can be a powerful method to identify how the propensity of the critical first step of NO dissociation can be increased. The testing of such concepts with atomic detail can be of great help in guiding the choices in rational catalyst design.
对具有明确组成原子数量和元素组成的金属簇表面上与多相催化相关的反应进行研究，并完全控制其组成原子数量和元素组成，能够深入洞察金属与反应物之间的相互作用。我们在此回顾了在分子束中接近热条件下，主要涉及一氧化氮（NO）分子吸附在以铑为基础的簇上的实验和理论研究。我们展示了红外光谱表征如何至少对前三个NO分子给出关于NO与簇结合性质的信息。热脱附光谱这一补充技术揭示了在何种温度下簇表面上的多个NO分子脱附或结合形成铑氧化物并随后消除氮。簇元素组成的变化可能是一种强大的方法，用于确定如何提高NO解离关键第一步的倾向。以原子细节对这些概念进行测试，对于指导合理催化剂设计中的选择可能会有很大帮助。
