Towards Atomically Precise Supported Catalysts from Monolayer‐Protected Clusters: The Critical Role of the Support
Alessandro Longo, Ewoud J. J. de Boed, Nisha Mammen, Marte van der Linden, Karoliina Honkala, Hannu Häkkinen, Petra E. de Jongh, Baira Donoeva
Abstract
Abstract Controlling the size and uniformity of metal clusters with atomic precision is essential for fine‐tuning their catalytic properties, however for clusters deposited on supports, such control is challenging. Here, by combining X‐ray absorption spectroscopy and density functional theory calculations, it is shown that supports play a crucial role in the evolution of monolayer‐protected clusters into catalysts. Based on the acidic nature of the support, cluster‐support interactions lead either to fragmentation of the cluster into isolated Au–ligand species or ligand‐free metallic Au 0 clusters. On Lewis acidic supports that bind metals strongly, the latter transformation occurs while preserving the original size of the metal cluster, as demonstrated for various Au n sizes. These findings underline the role of the support in the design of supported catalysts and represent an important step toward the synthesis of atomically precise supported nanomaterials with tailored physico‐chemical properties.