Correcting the Hydrogen Diffusion Limitation in Rotating Disk Electrode Measurements of Hydrogen Evolution Reaction Kinetics

Author(s)Zheng, Jie
Author(s)Yan, Yushan
Author(s)Xu, Bingjun
Ordered AuthorJie Zheng, Yushan Yan, and Bingjun Xu
UD AuthorZheng, Jieen_US
UD AuthorYan, Yushanen_US
UD AuthorXu, Bingjunen_US
Date Accessioned2015-12-22T16:18:12Z
Date Available2015-12-22T16:18:12Z
Copyright DateCopyright © The Author(s) 2015en_US
Publication Date2015-10-10
DescriptionPulsiher's PDFen_US
AbstractRotating disk electrode (RDE) method is widely employed in studies on the hydrogen oxidation/evolution reaction (HOR/HER) owing to its well-defined mass transport behaviors. While it is accepted that the measured HOR current is controlled by both the electrode kinetics and the diffusion of H2, HER is typically assumed to be free of diffusion limitation. Here we demonstrate that HER could also be diffusion limited when the electrode kinetics is fast, as evidenced by the rotation speed dependent HER current on Pt in acid (pH = 1) and the overlap of the HER polarization curve with the concentration overpotential curve. The HER diffusion limitation originates from the insufficient mass transport of produced H2 from the electrode surface to the bulk electrolyte and the highly reversible nature of HOR/HER. Kinetic analyses based on HER polarization curves on Pt in acid without correcting for the diffusion limitation could lead to inaccurate Tafel slopes and mechanistic interpretations, and significantly underestimated HER activities. A general data analysis protocol based on the reversible Koutecky-Levich equation is developed to obtain accurate kinetic information of HOR/HER even when electrode kinetics is facile. This new method is compared with other existing methods on Pt disk electrodes at different pHs and thin-film electrodes with different Pt loadings.en_US
DepartmentUniversity of Delaware. Center for Catalytic Science & Technology.en_US
CitationZheng, Jie, Yushan Yan, and Bingjun Xu. "Correcting the Hydrogen Diffusion Limitation in Rotating Disk Electrode Measurements of Hydrogen Evolution Reaction Kinetics." Journal of The Electrochemical Society 162.14 (2015): F1470-F1481.en_US
DOI10.1149/2.0501514jesen_US
ISSN0013-4651 ; e-1945-7111en_US
URLhttp://udspace.udel.edu/handle/19716/17340
Languageen_USen_US
PublisherThe Electrochemical Societyen_US
dc.rightsCC BY-NC-ND 4.0 http://creativecommons.org/licenses/by-nc-nd/4.0/en_US
dc.sourceJournal of The Electrochemical Societyen_US
dc.source.urihttp://jes.ecsdl.org/en_US
TitleCorrecting the Hydrogen Diffusion Limitation in Rotating Disk Electrode Measurements of Hydrogen Evolution Reaction Kineticsen_US
TypeArticleen_US
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