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Near-surface ion distribution and buffer effects during electrochemical reactions
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Auinger, Michael, Katsounaros, Ioannis, Meier, Josef C., Klemm, Sebastian O., Biedermann, P. Ulrich, Topalov, Angel A., Rohwerder, Michael and Mayrhofer, Karl J. J. (2011) Near-surface ion distribution and buffer effects during electrochemical reactions. Physical Chemistry Chemical Physics, Volume 13 (Number 36). Article number 16384. doi:10.1039/c1cp21717h ISSN 1463-9076.
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Official URL: http://dx.doi.org/10.1039/C1CP21717H
Abstract
The near-surface ion distribution at the solid–liquid interface during the Hydrogen Oxidation Reaction (HOR)/Hydrogen Evolution Reaction (HER) on a rotating platinum disc electrode is demonstrated in this work. The relation between reaction rate, mass transport and the resulting surface pH-value is used to theoretically predict cyclic voltammetry behaviour using only thermodynamic and diffusion data obtained from the literature, which were confirmed by experimental measurements. The effect of buffer addition on the current signal, the surface pH and the ion distribution is quantitatively described by analytical solutions and the fragility of the surface pH during reactions that form or consume H+ in near-neutral unbuffered solutions or poorly buffered media is highlighted. While the ideal conditions utilized in this fundamental study cannot be directly applied to real scenarios, they do provide a basic understanding of the surface pH concept for more complex heterogeneous reactions.
| Item Type: | Journal Article | ||||||||
|---|---|---|---|---|---|---|---|---|---|
| Divisions: | Faculty of Science, Engineering and Medicine > Engineering > WMG (Formerly the Warwick Manufacturing Group) | ||||||||
| Journal or Publication Title: | Physical Chemistry Chemical Physics | ||||||||
| Publisher: | Royal Society of Chemistry | ||||||||
| ISSN: | 1463-9076 | ||||||||
| Official Date: | September 2011 | ||||||||
| Dates: |
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| Volume: | Volume 13 | ||||||||
| Number: | Number 36 | ||||||||
| Article Number: | Article number 16384 | ||||||||
| DOI: | 10.1039/c1cp21717h | ||||||||
| Status: | Peer Reviewed | ||||||||
| Publication Status: | Published | ||||||||
| Access rights to Published version: | Restricted or Subscription Access |
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