Theoretical and Experimental Insights into the Origin of the Catalytic Activity of Subnanometric Gold Clusters: Attempts to Predict Reactivity with Clusters and Nanoparticles of Gold

Particle size is one of the key parameters determining the unexpected catalytic activity of gold, with reactivity improving as the particle gets smaller. While this is valid In the 1-5 nm range, chemists are now investigating the influence of particle size in the subnanometer regime. This is due to recent advances in both characterization techniques and synthetic routes capable of stabilizing these size-controlled gold dusters. Researchers reported in early studies that small clusters or aggregates of a few atoms can be extremely active in some reactions, while 1 2 nm nanoparticles are catalytically more efficient for other reactions. Furthermore, the possibility that small gold dusters generated in situ from gold salts or complexes could be the real active species in homogeneous gold-catalyzed organic reactions should be considered. In this Account we address two questions. First, what is the origin of the enhanced reactivity of gold dusters on the subnanometer scale? And second, how can we predict the reactions where small clusters should work better than larger nanoparticles? Both geometric factors and electronic or quantum size effects become Important in the subnanometer regime. Geometric reasons play a key role in hydrogenation reactions, where only accessible low coordinated neutral Au atoms are needed to dissodate H-2. The quantum size effects of gold dusters are important as well, as dusters formed by only a few atoms have discrete molecule-like electronic states and their chemical reactivity is related to interactions between the duster's frontier molecular orbitals and those of the reactant molecules. From first principles calculations, we predict an enhanced reactivity of small planar dusters for reactions involving activation of CC multiple bonds in alkenes and alkynes through Lewis acid base interactions, and a better catalytic performance of 3D gold nanoparticles in redox reactions involving bond dissociation by oxidative addition and new bond formation by reductive elimination. In oxidation reactions with molecular O-2, initial dissociation of O-2 Into basic oxygen atoms would be more effectively catalyzed by gold nanoparticles of similar to 1 nm diameter. In contrast, small planar clusters should be more active for reactions following a radical pathway involving peroxo or hydroperoxo intermediates. We have experimentally confirmed these predictions for a series of Lewis acid and oxidation reactions catalyzed by gold clusters and nanoparticles either in solution or supported on solid carriers.