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Enhanced electrocatalysis of the oxygen reduction reaction based on patterning of platinum surfaces with cyanide

Nature Chemistry volume 2, pages 880–885 (2010)Cite this article

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Abstract

The slow rate of the oxygen reduction reaction in the phosphoric acid fuel cell is the main factor limiting its wide application. Here, we present an approach that can be used for the rational design of cathode catalysts with potential use in phosphoric acid fuel cells, or in any environments containing strongly adsorbing tetrahedral anions. This approach is based on molecular patterning of platinum surfaces with cyanide adsorbates that can efficiently block the sites for adsorption of spectator anions while the oxygen reduction reaction proceeds unhindered. We also demonstrate that, depending on the supporting electrolyte anions and cations, on the same CN-covered Pt(111) surface, the oxygen reduction reaction activities can range from a 25-fold increase to a 50-fold decrease. This behaviour is discussed in the light of the role of covalent and non-covalent interactions in controlling the ensemble of platinum active sites required for high turn over rates of the oxygen reduction reaction.

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Figure 1: Electrochemical measurements on CN-modified and unmodified Pt(111) surfaces in solutions containing strongly adsorbing sulfuric and phosphoric acid anions.
Figure 2: Electrochemical measurements on CN-modified and unmodified Pt(111) surfaces in solutions containing weakly adsorbing perchloric acid anions and hydrated alkali metal cations.
Figure 3: Proposed models for selective adsorption of spectator species and reactants and schematic presentation of the availability of platinum surface atoms for adsorption of O2 molecules on CN-free and CN-covered Pt(111).

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Change history

  • 26 August 2010

    In the version of this Article originally published, the second author's surname was incorrectly spelt, it should have read María Escudero-Escribano. This has now been corrected on all versions of the Article.

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Acknowledgements

This work was supported by the Director, Office of Science, Office of Basic Energy Sciences, Division of Materials Sciences, US Department of Energy, under contract no. DE-AC02-06CH11357, and by the DGI (Ministerio de Educación y Ciencia) under project CTQ2006-02109. M.E. acknowledges an FPI fellowship from the DGI and an accommodation grant at the Residencia de Estudiantes from the Madrid City Council.

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Authors and Affiliations

  1. Materials Science Division, Argonne National Laboratory, Argonne, 60439, Illinois, USA

    Dusan Strmcnik, Kensaku Kodama, Vojislav R. Stamenkovic & Nenad M. Marković

  2. Instituto de Química Física, ‘Rocasolano’, CSIC, C. Serrano, 119, Madrid, E-28006, Spain

    María Escudero-Escribano & Angel Cuesta

  3. Toyota Central R&D Labs., Inc., 480-1192, Japan

    Kensaku Kodama

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  1. Dusan Strmcnik
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  2. María Escudero-Escribano
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Correspondence to Angel Cuesta or Nenad M. Marković.

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Strmcnik, D., Escudero-Escribano, M., Kodama, K. et al. Enhanced electrocatalysis of the oxygen reduction reaction based on patterning of platinum surfaces with cyanide. Nature Chem 2, 880–885 (2010). https://doi.org/10.1038/nchem.771

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