Towards Atomically Precise Supported Catalysts from Monolayer-Protected Clusters: The Critical Role of the Support.

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 clusters.