title: Exceptional oxidation activity with size-controlled supported gold clusters of low atomicity.
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.
authors: Instituto de Tecnología Química, Universidad Politécnica de Valencia-Consejo Superior de Investigaciones Científicas (UPV-CSIC), Av. de los Naranjos s/n, 46022 Valencia, Spain.
authors: Avelino
authors: A
authors: Corma
authors: Patricia
authors: P
authors: Concepción
authors: Mercedes
authors: M
authors: Boronat
authors: Maria J
authors: MJ
authors: Sabater
authors: Javier
authors: J
authors: Navas
authors: Miguel José
authors: MJ
authors: Yacaman
authors: Eduardo
authors: E
authors: Larios
authors: Alvaro
authors: A
authors: Posadas
authors: M Arturo
authors: MA
authors: López-Quintela
authors: David
authors: D
authors: Buceta
authors: Ernest
authors: E
authors: Mendoza
authors: Gemma
authors: G
authors: Guilera
authors: Alvaro
authors: A
authors: Mayoral
mesh_terms: D002384:Catalysis; D004220:Disulfides / Q000737:chemistry; D006046:Gold / Q000737:chemistry*; D053768:Metal Nanoparticles / Q000737:chemistry / Q000648:ultrastructure; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D010636:Phenols / Q000737:chemistry; D013438:Sulfhydryl Compounds / Q000737:chemistry
chemical_list: D004220:Disulfides; D010636:Phenols; D013438:Sulfhydryl Compounds; D006046:Gold; C042983:thiophenol; D010100:Oxygen
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