Gold Cluster Catalysis: A variety of gold salts and complexes have been used to catalyze different organic reactions. Often, the catalytic rates for these reactions are similar. Oliver-Meseguer et al. (p. 1452 ; see the Perspective by Hashmi ) observed an induction period for the onset of catalysis of organic reactions, such as the ester-assisted hydration of alkynes, for different gold salts and complexes. Mass spectrometry and absorption spectroscopy revealed that small gold clusters (three to ten atoms) formed during these induction periods and are likely to represent the active catalysts. The catalytic reaction rates could be extremely high—up to 10 ⁵ turnovers of the catalyst per hour.

Noble metals supported on reducible oxides, like CoO_x and TiO_x, exhibit superior activity in many chemical reactions, but the origin of the increased activity is not well understood. To answer this question we studied thin films of CoO_x supported on an Au(111) single crystal surface as a model for the CO oxidation reaction. We show that three reaction regimes exist in response to chemical and topographic restructuring of the CoO_x catalyst as a function of reactant gas phase CO/O₂ stoichiometry and temperature. Under oxygen-lean conditions and moderate temperatures (≤150 °C), partially oxidized films (CoO_x<1) containing Co⁰ were found to be efficient catalysts. In contrast, stoichiometric CoO films containing only Co²⁺ form carbonates in the presence of CO that poison the reaction below 300 °C. Under oxygen-rich conditions a more oxidized catalyst phase (CoO_x>1) forms containing Co³⁺ species that are effective in a wide temperature range. Resonant photoemission spectroscopy (ResPES) revealed the unique role of Co³⁺ sites in catalyzing the CO oxidation. Density function theory (DFT) calculations provided deeper insights into the pathway and free energy barriers for the reactions on these oxide phases. These findings in this work highlight the versatility of catalysts and their evolution to form different active phases, both topological and chemically, in response to reaction conditions exposing a new paradigm in the catalyst structure during operation.