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Pseudo-single crystal electrochemistry on polycrystalline electrodes : visualizing activity at grains and grain boundaries on platinum for the Fe2+/Fe3+ redox reaction
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Aaronson, Barak D. B., Chen, Chang-Hui, Li, Hongjiao, Koper, Marc T. M., Lai, Stanley Chi Shing and Unwin, Patrick R. (2013) Pseudo-single crystal electrochemistry on polycrystalline electrodes : visualizing activity at grains and grain boundaries on platinum for the Fe2+/Fe3+ redox reaction. Journal of the American Chemical Society, Volume 135 (Number 10). pp. 3873-3880. doi:10.1021/ja310632k ISSN 0002-7863.
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WRAP_Aaronson, JACS, 2013.pdf - Accepted Version Download (928Kb) | Preview |
Official URL: http://dx.doi.org/10.1021/ja310632k
Abstract
The influence of electrode surface structure on electrochemical reaction rates and mechanisms is a major theme in electrochemical research, especially as electrodes with inherent structural heterogeneities are used ubiquitously. Yet, probing local electrochemistry and surface structure at complex surfaces is challenging. In this paper, high spatial resolution scanning electrochemical cell microscopy (SECCM) complemented with electron backscatter diffraction (EBSD) is demonstrated as a means of performing ‘pseudo-single-crystal’ electrochemical measurements at individual grains of a polycrystalline platinum electrode, while also allowing grain boundaries to be probed. Using the Fe2+/3+ couple as an illustrative case, a strong correlation is found between local surface structure and electrochemical activity. Variations in electrochemical activity for individual high index grains, visualized in a weakly adsorbing perchlorate medium, show that there is higher activity on grains with a significant (101) orientation contribution, compared to those with (001) and (111) contribution, consistent with findings on single-crystal electrodes. Interestingly, for Fe2+ oxidation in a sulfate medium a different pattern of activity emerges. Here, SECCM reveals only minor variations in activity between individual grains, again consistent with single-crystal studies, with a greatly enhanced activity at grain boundaries. This suggests that these sites may contribute significantly to the overall electrochemical behavior measured on the macroscale.
Item Type: | Journal Article | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||
Library of Congress Subject Headings (LCSH): | Electrochemistry , High resolution electron microscopy, Electrons -- Backscattering | ||||
Journal or Publication Title: | Journal of the American Chemical Society | ||||
Publisher: | American Chemical Society | ||||
ISSN: | 0002-7863 | ||||
Official Date: | 13 March 2013 | ||||
Dates: |
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Volume: | Volume 135 | ||||
Number: | Number 10 | ||||
Page Range: | pp. 3873-3880 | ||||
DOI: | 10.1021/ja310632k | ||||
Status: | Peer Reviewed | ||||
Publication Status: | Published | ||||
Access rights to Published version: | Restricted or Subscription Access | ||||
Date of first compliant deposit: | 24 December 2015 | ||||
Date of first compliant Open Access: | 24 December 2015 | ||||
Funder: | European Research Council (ERC), Marie Curie Intra-European Fellowship (IEF), China Scholarship Council (CSC) | ||||
Grant number: | ERC-2009-AdG247143 (ERC), 275450 (MCIEF) |
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