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Enhanced oxidation of nanoparticles through strain-mediated ionic transport

Nature Materials volume 13, pages 26–30 (2014)Cite this article

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Abstract

Geometry and confinement effects at the nanoscale can result in substantial modifications to a material’s properties with significant consequences in terms of chemical reactivity, biocompatibility and toxicity1,2. Although benefiting applications across a diverse array of environmental and technological settings, the long-term effects of these changes, for example in the reaction of metallic nanoparticles under atmospheric conditions, are not well understood. Here, we use the unprecedented resolution attainable with aberration-corrected scanning transmission electron microscopy3 to study the oxidation of cuboid Fe nanoparticles. Performing strain analysis at the atomic level, we reveal that strain gradients induced in the confined oxide shell by the nanoparticle geometry enhance the transport of diffusing species, ultimately driving oxide domain formation and the shape evolution of the particle. We conjecture that such a strain-gradient-enhanced mass transport mechanism may prove essential for understanding the reaction of nanoparticles with gases in general, and for providing deeper insight into ionic conductivity in strained nanostructures.

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Figure 1: Evaluation of a high-resolution Z-contrast image of an Fe/Fe oxide core–shell nanoparticle.
Figure 2: Beyond Cabrera–Mott initial oxidation to a fully oxidized nanoparticle.
Figure 3: Analysis of strain at the Fe/Fe oxide interface.
Figure 4: Strain gradients at the nanoscale enhance the rate of metal oxidation.

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Change history

  • 11 November 2013

    In the version of this Letter originally published online, part of the address of the fifth affiliation was incorrect; it should have read "Frederick Seitz Materials Research Laboratory". This error has now been corrected in all versions of the Letter.

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Acknowledgements

We acknowledge support by the Max-Kade foundation for a Visiting Professorship stipend to one of the authors (R.K.) as well as financial support by the World University Network (WUN) for the collaboration with the University of Illinois at Champaign-Urbana (R.K.). The Engineering and Physical Sciences Research Council (EPSRC) are also acknowledged for funding the initial stages of this project (EP/D034604/1). Electron microscopy was carried out at the Materials Research Laboratory Central Facilities at the University of Illinois at Urbana Champaign and the York JEOL Nanocentre. We are grateful to E. Rabkin for critically reading the manuscript. O.H. gratefully acknowledges support from a Marie Curie Intra European Fellowship within the 7th European Community Framework Programme under grant agreement PIEF-GA-2010-273014.

Author information

Authors and Affiliations

  1. Department of Physics, University of York, York YO10 5DD, UK

    Andrew Pratt, Leonardo Lari, Ondrej Hovorka, Charles Woffinden, Steve P. Tear & Roland Kröger

  2. International Center for Young Scientists, National Institute for Materials Science, 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan

    Andrew Pratt

  3. York JEOL Nanocentre, University of York, York YO10 5BR, UK

    Leonardo Lari

  4. Faculty of Engineering and the Environment, University of Southampton, Southampton SO17 1BJ, UK

    Ondrej Hovorka

  5. University of Illinois at Urbana-Champaign, Frederick Seitz Materials Research Laboratory, Illinois 61801, USA

    Amish Shah

  6. Department of Physics and Astronomy, University of Leicester, Leicester LH1 7RH, UK

    Chris Binns

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  1. Andrew Pratt
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Contributions

R.K., A.P. and C.B. planned the initial experiments led by R.K. Deposition of Fe nanoparticles was carried out by A.P., C.W. and S.P.T. Electron microscopy and EELS were performed by A.S. and R.K. in Illinois and L.L. and R.K. in York. The atomic-level strain analysis procedure used was developed by R.K. with additional strain analysis by A.P. Theoretical models were developed analytically by O.H. and numerically by R.K. The manuscript was prepared by A.P. and R.K.

Corresponding authors

Correspondence to Andrew Pratt or Roland Kröger.

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The authors declare no competing financial interests.

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Pratt, A., Lari, L., Hovorka, O. et al. Enhanced oxidation of nanoparticles through strain-mediated ionic transport. Nature Mater 13, 26–30 (2014). https://doi.org/10.1038/nmat3785

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