Tuning the Reactivity of Small Metal Clusters by Heteroatom Doping

The reactivity of small metallic clusters, nanoparticles composed of a countable number of atoms (typically up to ∼100 atoms), has attracted much attention due to the fascinating properties these objects possess toward a variety of molecules. Cluster reactivity often is significantly different from the homologous bulk, with gold as prototypical example. Bulk gold is the noblest of all metals, whereas small gold clusters react with carbon monoxide, molecular oxygen, and hydrocarbons, among others. Furthermore, cluster reactivity is strongly size and composition dependent, allowing a wide range of tuning possibilities. The study of cluster reactivity usually follows two routes of investigation. In the first, research aims for fundamental understanding of mechanisms, mainly driven by curiosity. One consequence of the inherent small size of a cluster is that atoms can arrange themselves very differently from the crystallographic structure of the homologous bulk. In addition, quantum confinement effects dominate the electronic structure of a cluster with atom-like electronic shells instead of the electronic bands in bulk. These features result in a very rich and size-dependent interaction of a cluster with small molecules, governed by a fine interplay between the geometry and the electronic structure of the system. An alternative research approach uses the investigation of chemical reactions of isolated small clusters in the gas phase as model systems for the reactions taking place in more complex systems. This offers several advantages compared to more conventional methods and techniques used to study such complex systems. First, clusters can be produced under well-defined conditions, with control over size, composition, and charge state. Second, clusters in the gas phase solely interact with the molecule(s) chosen by the researcher, since contaminations are limited by the high vacuum conditions of the experiments. Third, due to the small number of atoms involved, detailed quantum chemical calculations can be performed on the systems under investigation. Thus, even though gas phase clusters differ significantly in size and in environmental conditions from those encountered, for example, in industrial catalysis, they can be used to unravel the complicated nature of a metal-molecule chemical bonding process. In this Account, both routes of investigation are discussed. The nature of the interaction between small gas phase clusters with diverse molecules is described, stressing the broader relevance of these studies. Particular emphasis is given to the effect of heteroatom doping. By adding a different element to a cluster, its geometric and electronic structure is modified, thereby altering its reactivity. Specifically, the effect of varying size and composition of doped gold, platinum, and aluminum clusters on their reactivity toward diverse molecules, relevant for catalytic applications, is discussed. Most studies presented here combine experiments based on mass spectrometric techniques with density functional theory calculations, allowing a deep understanding of the reaction mechanisms at a molecular level.