Activation of atom-precise clusters for catalysis

The use of atom-precise, ligand-protected metal clusters has exceptional promise towards the fabrication of model supported-nanoparticle heterogeneous catalysts which have controlled sizes and compositions. One major challenge in the field involves the ease at which metallic clusters sinter upon removal of protected ligands, thus destroying the structural integrity of the model system. This review focuses on methods used to activate atom-precise thiolate-stabilized clusters for heterogeneous catalysis, and strategies that can be used to mitigate sintering. Thermal activation is the most commonly employed approach to activate atom-precise metal clusters, though a variety of chemical and photochemical activation strategies have also been reported. Material chemistry methods that can mitigate sintering are also explored, which include overcoating of clusters with metal oxide supports fabricated by sol-gel chemistry or atomic layer deposition of thin oxide films or encapsulating clusters within porous supports. In addition to focusing on the preservation of the size and morphology of deprotected metal clusters, the fate of the removed ligands is also explored, because detached and/or oxidized ligands can also greatly influence the overall properties of the catalyst systems. We also show that modern characterization techniques such as X-ray absorption spectroscopy and high-resolution electron microscopy have the capacity to enable careful monitoring of particle sintering upon activation of metal clusters.