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Measuring oxygen reduction/evolution reactions on the nanoscale

Nature Chemistry volume 3, pages 707–713 (2011)Cite this article

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Abstract

The efficiency of fuel cells and metal–air batteries is significantly limited by the activation of oxygen reduction and evolution reactions. Despite the well-recognized role of oxygen reaction kinetics on the viability of energy technologies, the governing mechanisms remain elusive and until now have been addressable only by macroscopic studies. This lack of nanoscale understanding precludes optimization of material architecture. Here, we report direct measurements of oxygen reduction/evolution reactions and oxygen vacancy diffusion on oxygen-ion conductive solid surfaces with sub-10 nm resolution. In electrochemical strain microscopy, the biased scanning probe microscopy tip acts as a moving, electrocatalytically active probe exploring local electrochemical activity. The probe concentrates an electric field in a nanometre-scale volume of material, and bias-induced, picometre-level surface displacements provide information on local electrochemical processes. Systematic mapping of oxygen activity on bare and platinum-functionalized yttria-stabilized zirconia surfaces is demonstrated. This approach allows direct visualization of the oxygen reduction/evolution reaction activation process at the triple-phase boundary, and can be extended to a broad spectrum of oxygen-conductive and electrocatalytic materials.

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Figure 1: ESM technique for measurement of activity on the nanoscale.
Figure 2: Dynamic ESM—separating local kinetics from thermodynamics.
Figure 3: Effects of bias magnitude and tip coating on local ESM.
Figure 4: Numerical modelling of electrochemical potentials at the tip–surface junction.
Figure 5: Local ESM mapping on an YSZ surface with nanometre-scale resolution.
Figure 6: Mapping electrochemical activity near a triple-phase boundary.

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Acknowledgements

This research was conducted (A.K., S.J., S.V.K.) at the Center for Nanophase Materials Sciences, which is sponsored at the Oak Ridge National Laboratory by the Scientific User Facilities Division, US Department of Energy. F.C. acknowledges support from a Marie Curie Reintegration Grant FastCell-256583. The authors are grateful to P. Rack and J. Fowlkes for deposition of platinum nanoparticles.

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Authors and Affiliations

  1. The Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, 37831, Tennessee, USA

    Amit Kumar, Sergei V. Kalinin & Stephen Jesse

  2. Heidelberg Graduate School of Mathematical and Computational Methods for the Sciences, Institut für Angewandte Mathematik, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 293, Heidelberg, 69120, Germany

    Francesco Ciucci

  3. Institute of Semiconductor Physics, National Academy of Science of Ukraine, 41, pr. Nauki, Kiev, 03028, Ukraine

    Anna N. Morozovska

Authors
  1. Amit Kumar
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  2. Francesco Ciucci
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  3. Anna N. Morozovska
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  4. Sergei V. Kalinin
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Contributions

S.J. and S.V.K. proposed the concept. S.J. and A.K. designed the experiments, which were performed by A.K.. S.J. developed the spectroscopic measurement technique and analysis tools. The semi-analytical calculations were performed by A.N.M., and numerical modelling of the electrochemical potential was carried out by F.C. The article was written by A.K. and S.V.K. All authors discussed the results and commented on the manuscript.

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Correspondence to Amit Kumar or Sergei V. Kalinin.

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The authors declare no competing financial interests.

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Kumar, A., Ciucci, F., Morozovska, A. et al. Measuring oxygen reduction/evolution reactions on the nanoscale. Nature Chem 3, 707–713 (2011). https://doi.org/10.1038/nchem.1112

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