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Size-specific catalytic activity of platinum clusters enhances oxygen reduction reactions

Nature Chemistry volume 1, pages 397–402 (2009)Cite this article

A Corrigendum to this article was published on 01 September 2010

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Abstract

Colloidal platinum nanoparticles with diameters of 2–5 nm on carbon supports are currently regarded as the best catalysts for the oxygen reduction reaction. However, the particle size is limited by the conventional preparation methods that are used to synthesize small platinum particles; the inherent activity of ultrasmall nanoparticles has not yet been revealed. We present a practical synthesis for ultrafine subnanometre platinum clusters using a spherical macromolecular template with no disorder in molecular weight or structure. The template, a phenylazomethine dendrimer, offers control of the number of metal complexes in an assembly through stepwise complexation, allowing the complexes to accumulate in discrete nano-cages. Subsequent reduction of Pt(IV) chloride to Pt(0) results in the formation of platinum clusters composed of a defined number of atoms. As a result of exceptionally small particle size, the clusters exhibit very high catalytic activity for the four-electron reduction of oxygen molecules.

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Figure 1: Phenylazomethine dendrimers as a template for metal cluster assembly.
Figure 2: Schematic representation of platinum cluster synthesis.
Figure 3: Electrochemical reduction of O2 using electrodes modified with platinum clusters as catalysts.

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Change history

  • 23 August 2010

    In the version of this Article originally published, the descriptions about data analysis of the electrocatalysis in the Methods section were incorrect. This has been corrected in the HTML and PDF versions of the Article.

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Acknowledgements

This work was partially supported by CREST from the Japan Science and Technology Agency, and a Grants-in-Aid for Scientific Research (Nos. 19205020, 19022034) from the Ministry of Education, Culture, Sports, Science and Technology, Japan. The XAFS measurements were performed under the approval of the Photon Factory Program Advisory Committee (Proposal No. 2007G160).

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Science and Technology, Keio University, Yokohama, 223-8522, Japan

    Kimihisa Yamamoto, Takane Imaoka, Osamu Enoki, Hideaki Katoh, Masahiro Takenaga & Atsunori Sonoi

  2. Department of Science, College of Liberal Arts, International Christian University, Mitaka, 181-8585, Japan

    Wang-Jae Chun

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  1. Kimihisa Yamamoto
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  2. Takane Imaoka
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Contributions

O.E., H.K. and M.T. prepared clusters and modified electrodes. M.T. and T.I. carried out electrochemical measurements. W.C., T.I. and A.S. carried out XAFS experiments. W.C. analysed the EXAFS spectra. T.I. H.K. and K.Y. conceived experiments, designed experimental procedures and co-wrote the manuscript. K.Y. directed the research.

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Correspondence to Kimihisa Yamamoto.

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Yamamoto, K., Imaoka, T., Chun, WJ. et al. Size-specific catalytic activity of platinum clusters enhances oxygen reduction reactions. Nature Chem 1, 397–402 (2009). https://doi.org/10.1038/nchem.288

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