Structural, Electronic, and Impurity-doping Effects in Catalytically Active Gold Nanoclusters and Nanostructures

Metal clusters exhibit unique size-dependent physical and chemical properties that differ from those of bulk materials or large particles. Here we discuss recent theoretical investigations of the catalytic properties of free and MgO-supported gold clusters. The catalytic activity of gold clusters depends sensitively on the environment, charge state, and chemical composition of the catalyst. Relativistic bonding effects stabilize large planar structures for gas-phase gold clusters, and non-compact ?quasiplanar? structures are present as important isomers also for surface-supported clusters. The hybridization of the atomic 5d and 6s states is significantly enhanced by the relativistic effects, and large spatial variations in the nature of the local electronic structure make the low-coordinated gold atoms preferable adsorption sites for oxygen molecules. The adsorbed oxygen molecules are activated to superoxo- and peroxo-states via charge-transfer from gold, and Eley-Rideal and Langmuir-Hinshelwood reactions with CO proceed via low-barrier formation of intermediates, which do not require O-O dissociation as precursors. This facilitates the low-temperature (below 300 K) activity of gold nanocatalysts in CO oxidation. Other gold nanostructures, such as mono-atomic gold nanowires, may also become important prototype systems in chemical sensing and nanocatalysis; here we show that they are active promoters of hydrogen dissociation.