Correcting the Hydrogen Diffusion Limitation in Rotating Disk Electrode Measurements of Hydrogen Evolution Reaction Kinetics
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Rotating 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 H 2 , 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 H 2 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.
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Competition between HER and hydrogen oxidation reactions (HOR) occurs at low potentials due to undiffused H2 gas, leading to reduced measured mass activity.
“Additionally, competition between HER and hydrogen oxidation reactions (HOR) occurs at low potentials due to undiffused H2 gas, leading to reduced measured mass activity.[91]”
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- Authors
- Zheng, J., Yan, Y., & Xu, B.
- Affiliations
- University of Delaware (US)
- Venue
- Journal of The Electrochemical Society
- Publisher
- The Electrochemical Society
- Published
- 2015
- Volume
- 162
- Issue
- 14
- Pages
- F1470-F1481
- ISSN
- 0013-4651 (ISSN-L)
- 1945-7111
- OpenAlex
- W2242312979
- Cited by
- 176
- References
- 33
- Citations by year
- 2026: 12 · 2025: 20 · 2024: 23 · 2023: 22 · 2022: 20 · 2021: 19 · 2020: 20 · 2019: 9 · 2018: 10 · 2017: 12 · 2016: 9
- FWCI
- 3.06
- Type
- journal article
- Language
- en
- Open access
- hybrid
- doi.org
- Licence
- cc-by-nc-nd
- Locations
- Journal of The Electrochemical Society (publishedVersion, cc-by-nc-nd)
- Library, Museums and Press - UDSpace (University of Delaware) (submittedVersion, cc-by-nc-nd)
- Funders
- U.S. Department of Energy
- University of Delaware Research Foundation
- University of Delaware
- Advanced Research Projects Agency
- Topics
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Electrocatalysts for Energy Conversion
- Physical Sciences › Engineering › Electrical and Electronic Engineering › Fuel Cells and Related Materials
- Physical Sciences › Materials Science › Materials Chemistry › Hydrogen Storage and Materials
- Keywords
- hydrogen evolution reaction, hydrogen oxidation, rotating disk electrode, diffusion limitation, mass transfer, Koutecky-Levich analysis, Tafel slope, platinum electrode, acidic electrolyte, polarization curves, concentration overpotential, reaction kinetics
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