Exceptional oxidation activity with size-controlled supported gold clusters of low atomicity
Top Cited Papers
- 4 August 2013
- journal article
- Published by Springer Science and Business Media LLC in Nature Chemistry
- Vol. 5 (9), 775-781
- https://doi.org/10.1038/nchem.1721
Abstract
The catalytic activity of gold depends on particle size, with the reactivity increasing as the particle diameter decreases. However, investigations into behaviour in the subnanometre regime (where gold exists as small clusters of a few atoms) began only recently with advances in synthesis and characterization techniques. Here we report an easy method to prepare isolated gold atoms supported on functionalized carbon nanotubes and their performance in the oxidation of thiophenol with O2. We show that single gold atoms are not active, but they aggregate under reaction conditions into gold clusters of low atomicity that exhibit a catalytic activity comparable to that of sulfhydryl oxidase enzymes. When clusters grow into larger nanoparticles, catalyst activity drops to zero. Theoretical calculations show that gold clusters are able to activate thiophenol and O2 simultaneously, and larger nanoparticles are passivated by strongly adsorbed thiolates. The combination of both reactants activation and facile product desorption makes gold clusters excellent catalysts.Keywords
This publication has 48 references indexed in Scilit:
- Propene epoxidation with O2 and H2: Identification of the most active gold clustersJournal of Catalysis, 2011
- Aerobic Oxidation of Cyclohexane Catalyzed by Size-Controlled Au Clusters on Hydroxyapatite: Size Effect in the Sub-2 nm RegimeACS Catalysis, 2010
- Gold Supported on Thin Oxide Films: From Single Atoms to NanoparticlesAccounts of Chemical Research, 2008
- Gold CatalysisAngewandte Chemie, 2006
- Catalytically Active Gold: From Nanoparticles to Ultrathin FilmsAccounts of Chemical Research, 2006
- Tunable gold catalysts for selective hydrocarbon oxidation under mild conditionsNature, 2005
- Catalysis by goldCatalysis Today, 2005
- On the origin of the catalytic activity of gold nanoparticles for low-temperature CO oxidationJournal of Catalysis, 2004
- Size- and support-dependency in the catalysis of goldCatalysis Today, 1997
- Low-Temperature Oxidation of CO over Gold Supported on TiO2, α-Fe2O3, and Co3O4Journal of Catalysis, 1993