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

Nature Chemistry volume 5, pages 775–781 (2013)Cite this article

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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.

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Figure 1: Identification of isolated gold atoms.
Figure 2: Oxidation of thiophenol to disulfide in the presence of O2.
Figure 3: Evolution of the gold species present on the catalyst.
Figure 4: Oxidation of thiophenol to disulfide in the presence of O2 catalysed by size-selected gold clusters.
Figure 5: Structures involved in the mechanism of disulfide formation catalysed by Au(I) species.
Figure 6: Reactivity of gold clusters of low atomicity.

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Acknowledgements

Financial support from the Spanish Science and Innovation Ministry (Consolider Ingenio 2010-MULTICAT CSD2009-00050, Subprograma de apoyo a Centros y Universidades de Excelencia Severo Ochoa SEV 2012 0267, MAT2011-28009 and MAT2010-20442 projects) and Xunta de Galicia (Grupos Ref.Comp.2010/41) is acknowledged. M.J.Y. and E.L. acknowledge the support of the National Centre for Research Resources (5 G12RR013646-12) and the National Institute on Minority Health and Health Disparities (G12MD007591) from the National Institutes of Health and of the National Science Foundation for support with grants DMR-1103730 and PREM: NSF PREM Grant # DMR 0934218. We also acknowledge the support of Consejo Nacional De Ciencia y Tecnología. J.N. expresses his gratitude to Consejo Superior de Investigaciones Científicas for a JAE Fellowship.

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Authors and Affiliations

  1. Instituto de Tecnología Química, Universidad Politécnica de Valencia-Consejo Superior de Investigaciones Científicas (UPV-CSIC), Av. de los Naranjos s/n, 46022, Valencia, Spain

    Avelino Corma, Patricia Concepción, Mercedes Boronat, Maria J. Sabater & Javier Navas

  2. Department of Physics, The University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas, 78249, USA

    Miguel José Yacaman, Eduardo Larios & Alvaro Posadas

  3. Departamento de Investigación en Polímeros y Materiales, Universidad de Sonora, Hermosillo, Sonora, México

    Eduardo Larios

  4. Department of Physical Chemistry, Faculty of Chemistry, Laboratory of Nanotechnology and Magnetism (NANOMAG) Research Technological Institute, University of Santiago de Compostela, E-15782, Santiago de Compostela, Spain

    M. Arturo López-Quintela & David Buceta

  5. Grup de Nanomaterials Aplicats, Centre de Recerca en Nanoenginyeria, Universitat Politècnica de Catalunya, c/Pascual i Vila 15, Barcelona, 08028, Spain

    Ernest Mendoza

  6. Experiments Division, ALBA Synchrotron, Crta. BP 1413, de Cerdanyola del Vallès a Sant Cugat del Vallès, 08290 Cerdanyola del Vallès, Barcelona, Spain

    Gemma Guilera

  7. Laboratorio de Microscopias Avanzadas, Instituto de Nanociencia de Aragon, Universidad de Zaragoza, Mariano Esquillor Edificio I+D, Zaragoza, 50018, Spain

    Alvaro Mayoral

Authors
  1. Avelino Corma
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Contributions

A.C. conceived, designed and directed the study and the analysis and interpretation of results. P.C. performed catalyst synthesis, characterization and testing. E.M. participated in catalyst synthesis. M.J.S. and J.N. carried out catalyst testing. M.B. designed and carried out the theoretical study. M.J.Y., E.L. and A.P. performed the HR-STEM characterization. M.A.L-Q. and D.B. synthesized and characterized the isolated size-controlled clusters. G.G. did the XAS measurements. A.M. collaborated in HR-STEM characterization. The manuscript was co-written by P.C., M.B. and A.C.

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Correspondence to Avelino Corma.

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Corma, A., Concepción, P., Boronat, M. et al. Exceptional oxidation activity with size-controlled supported gold clusters of low atomicity. Nature Chem 5, 775–781 (2013). https://doi.org/10.1038/nchem.1721

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