Exceptional oxidation activity with size-controlled supported gold clusters of low atomicity

[EN] 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 c...

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Bibliographic Details
Authors: Corma Canós, Avelino|||0000-0002-2232-3527, Concepción Heydorn, Patricia|||0000-0003-2058-3103, Boronat Zaragoza, Mercedes|||0000-0002-6211-5888, Sabater Picot, Mª José, Navas Escrig, Javier, Yacaman, Miguel José, Larios, Eduardo, Posadas, Álvaro, López Quintela, M. Arturo, Buceta, David, Mendoza, Ernest, Guilera, Gemma, Mayoral, Álvaro
Format: article
Publication Date:2013
Country:España
Institution:Universitat Politècnica de València (UPV)
Repository:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
Language:English
OAI Identifier:oai:riunet.upv.es:10251/67246
Online Access:https://riunet.upv.es/handle/10251/67246
Access Level:Open access
Keyword:Gold
Gold, clusters, atomicity, oxidation, disulfides
Clusters
Atomicity
Oxidation
Disulfides
QUIMICA ORGANICA
Description
Summary:[EN] 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 O-2. 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 O-2 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.

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