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Mass-selected nanoparticles of PtxY as model catalysts for oxygen electroreduction

Nature Chemistry volume 6, pages 732–738 (2014)Cite this article

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Abstract

Low-temperature fuel cells are limited by the oxygen reduction reaction, and their widespread implementation in automotive vehicles is hindered by the cost of platinum, currently the best-known catalyst for reducing oxygen in terms of both activity and stability. One solution is to decrease the amount of platinum required, for example by alloying, but without detrimentally affecting its properties. The alloy PtxY is known to be active and stable, but its synthesis in nanoparticulate form has proved challenging, which limits its further study. Herein we demonstrate the synthesis, characterization and catalyst testing of model PtxY nanoparticles prepared through the gas-aggregation technique. The catalysts reported here are highly active, with a mass activity of up to 3.05 A mgPt−1 at 0.9 V versus a reversible hydrogen electrode. Using a variety of characterization techniques, we show that the enhanced activity of PtxY over elemental platinum results exclusively from a compressive strain exerted on the platinum surface atoms by the alloy core.

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Figure 1: Surface characterization of the PtxY nanoparticles before and after ORR activity measurements.
Figure 2: Particle-size distributions and representative TEM micrographs for the PtxY catalysts.
Figure 3: Catalyst activity of PtxY in nanoparticles in comparison to Pt.
Figure 4: High-angle annular dark-field (HAADF)-STEM images and EDS elemental maps for PtxY 9 nm.
Figure 5: XAS analysis.

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Acknowledgements

The authors gratefully acknowledge financial support from the Danish Ministry of Science's UNIK initiative, Catalysis for Sustainable Energy. The Center for Individual Nanoparticle Functionality is supported by the Danish National Research Foundation (DNRF54). The A.P. Møller and Chastine Mc-Kinney Møller Foundation is gratefully acknowledged for its contribution towards the establishment of the Centre for Electron Nanoscopy in the Technical University of Denmark. The Interdisciplinary Centre for Electron Microscopy at École Polytechnique Fédérale de Lausanne is gratefully acknowledged for the use of the FEI Tecnai Osiris TEM. Support for this work was received from the Danish Council for Strategic Research's project NACORR (12-133817) and MEDLYS (10-093906). I.E.L.S. was supported by the ForskEL programme's project CATBOOSTER (2001-1-10669). D.N.M. is the recipient of a HC Ørsted postdoctoral fellowship. Part of this work is supported by Basic Energy Sciences, US Department of through the SUNCAT Center for Interface Science and Catalysis. This research was partly carried out at the Stanford Synchrotron Radiation Lightsource, a National User Facility operated by Stanford University on behalf of the Basic Energy Sciences, US Department of Energy. We thank J. Bargar, A. Mehta, R. Davis, M. Latimer and E. J. Nelson for support with the EXAFS instrumentation and for helpful discussions.

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Authors and Affiliations

  1. Department of Physics, Center for Individual Nanoparticle Functionality, Technical University of Denmark, Kgs Lyngby, DK-2800, Denmark

    Patricia Hernandez-Fernandez, Federico Masini, David N. McCarthy, Christian E. Strebel, Paolo Malacrida, Anders Nierhoff, Anders Bodin, Jane H. Nielsen, Ifan E. L. Stephens & Ib Chorkendorff

  2. SLAC National Accelerator Laboratory, 2575 Sand Hill Road, MS31, Menlo Park CA, 94025, USA

    Daniel Friebel, Anna M. Wise & Anders Nilsson

  3. Center for Electron Nanoscopy, Technical University of Denmark, Kgs Lyngby, DK-2800, Denmark

    Davide Deiana & Thomas W. Hansen

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  1. Patricia Hernandez-Fernandez
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Contributions

I.C. and I.E.L.S. conceived the experiments. P.H-F. performed the electrochemical experiments. F.M., D.N.M., C.E.S., P.M. and A.N. performed the UHV experiments. D.F., A.B. and A.M.W performed the XAS measurements. D.D. performed the microscopy. P.H-F. designed the figures. P.H-F. and I.E.L.S. wrote the first draft of the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Ifan E. L. Stephens or Ib Chorkendorff.

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Competing interests

I.C. and I.E.L.S. have a patent on the catalyst material PtxY, PCT/DK2010/050193. The other authors declare no competing financial interests.

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Hernandez-Fernandez, P., Masini, F., McCarthy, D. et al. Mass-selected nanoparticles of PtxY as model catalysts for oxygen electroreduction. Nature Chem 6, 732–738 (2014). https://doi.org/10.1038/nchem.2001

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