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Mesostructured thin films as electrocatalysts with tunable composition and surface morphology

Nature Materials volume 11, pages 1051–1058 (2012)Cite this article

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Abstract

Among the most challenging issues in technologies for electrochemical energy conversion are the insufficient activity of the catalysts for the oxygen reduction reaction, catalyst degradation and carbon-support corrosion. In an effort to address these barriers, we aimed towards carbon-free multi/bimetallic materials in the form of mesostructured thin films with tailored physical properties. We present here a new class of metallic materials with tunable near-surface composition, morphology and structure that have led to greatly improved affinity for the electrochemical reduction of oxygen. The level of activity for the oxygen reduction reaction established on mesostructured thin-film catalysts exceeds the highest value reported for bulk polycrystalline Pt bimetallic alloys, and is 20-fold more active than the present state-of-the-art Pt/C nanoscale catalyst.

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Figure 1: CV and STM images of Pt and Pt alloy 20-nm thin films deposited on a glassy carbon substrate.
Figure 2: HRSEM and TEM micrographs of the NSTF whiskers.
Figure 3: In situ transformation from nanostructured into mesostructured thin film during annealing.
Figure 4: CV on the Pt-based thin-film catalysts.
Figure 5: Activity map for the ORR obtained for different classes of Pt-based materials.

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Acknowledgements

The research was conducted at Argonne National Laboratory, which is a US Department of Energy Office of Science Laboratory operated by UChicago Argonne, LLC under contract no. DE-AC02-06CH11357. The portion of work related to extended single-crystalline and thin-film surfaces was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division. The portion of work exploring practical thin-film-based electrocatalysts was supported by the Office of Energy Efficiency and Renewable Energy, Fuel Cell Technologies Program. The authors thank Hitachi High Technologies America for the access to high-resolution electron microscopy facilities and J. Pearson and A. P. Paulikas for supporting thin film deposition experiments. V.R.S. is grateful to S. D. Bader and G.W. Crabtree for productive discussions.

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Author notes

  1. Dennis F. van der Vliet and Chao Wang: These authors contributed equally to this work

Authors and Affiliations

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

    Dennis F. van der Vliet, Chao Wang, Dusan Tripkovic, Dusan Strmcnik, Nenad M. Markovic & Vojislav R. Stamenkovic

  2. Hitachi High Technologies America, Pleasanton, California 94588, USA

    Xiao Feng Zhang

  3. Fuel Cell Components Program, 3M, St Paul, Minnesota 55144, USA

    Mark K. Debe & Radoslav T. Atanasoski

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  1. Dennis F. van der Vliet
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Contributions

D.F.V., C.W. and V.R.S. designed the experiments. C.W., D.F.V., D.T., D.S., X.F.Z., R.T.A., M.K.D. and V.R.S. carried out the experimental work. D.F.V., C.W., M.K.D., N.M.M. and V.R.S. discussed the results and V.R.S. wrote the manuscript.

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Correspondence to Dennis F. van der Vliet, Chao Wang or Vojislav R. Stamenkovic.

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van der Vliet, D., Wang, C., Tripkovic, D. et al. Mesostructured thin films as electrocatalysts with tunable composition and surface morphology. Nature Mater 11, 1051–1058 (2012). https://doi.org/10.1038/nmat3457

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