Hydrogen Oxidation and Evolution Reaction Kinetics on Platinum: Acid vs Alkaline Electrolytes
Open accessAbstract
The kinetics of the hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) on polycrystalline platinum [Pt(pc)] and high surface area carbon-supported platinum nanoparticles (Pt/C) were studied in 0.1 M KOH using rotating disk electrode (RDE) measurements. After corrections of noncompensated solution resistance from ac impedance spectroscopy and of hydrogen mass transport in the HOR branch, the kinetic current densities were fitted to the Butler–Volmer equation using a transfer coefficient of α = 0.5 , from which HOR/HER exchange current densities on Pt(pc) and Pt/C were obtained, and the HOR/HER mechanisms in alkaline solution were discussed. Unlike the HOR/HER rates on Pt electrodes in alkaline solution, the HOR/HER rates on a Pt electrode in 0.1 M HClO 4 were limited entirely by hydrogen diffusion, which renders the quantification of the HOR/HER kinetics impossible by conventional RDE measurements. The simulation of the hydrogen anode performance based on the specific exchange current densities of the HOR/HER at 80 ° C illustrates that in addition to the oxygen reduction reaction cell voltage loss on the cathode, the slow HOR kinetics are projected to cause significant anode potential losses in alkaline fuel cells for low platinum loadings ( 130 mV at 0.05 mg Pt / cm anode 2 and 1.5 A / cm anode 2 ), contrary to what is reported for proton exchange membrane fuel cells.
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HOR/HER activities in alkaline media are two orders of magnitude slower than those in acidic environment.
“However, the HOR/HER activities in alkaline media have been demonstrated two orders of magnitude slower than those in acidic environment [11,12].”
From Lamellar platinum–rhodium aerogels with superior electrocatalytic performance for both hydrogen oxidation and evolution reaction in alkaline environment (2019) · cites this paper as [12]
The Abstract (page unavailable) says prior microelectrode studies on platinum suggest HOR/HER exchange current densities are two orders of magnitude lower in alkaline than acidic electrolytes. The paper’s comparison section confirms slower kinetics in alkaline electrolyte, but its acid RDE measurements cannot quantify the exchange current density, so its own measurements do not demonstrate the precise two-order difference. (LLM, conf=0.82)
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- Authors
- Sheng, W., Gasteiger, H. A., & Shao-Horn, Y.
- Affiliations
- Massachusetts Institute of Technology (US)
- Technical University of Munich (DE)
- Venue
- Journal of The Electrochemical Society
- Publisher
- The Electrochemical Society
- Published
- 2010
- Volume
- 157
- Issue
- 11
- Pages
- B1529
- ISSN
- 0013-4651 (ISSN-L)
- OpenAlex
- W2116243685
- Cited by
- 1,829
- References
- 1
- Citations by year
- 2026: 118 · 2025: 151 · 2024: 156 · 2023: 163 · 2022: 142 · 2021: 132 · 2020: 177 · 2019: 158 · 2018: 138 · 2017: 154 · 2016: 114 · 2015: 96 · 2014: 61 · 2013: 39 · 2012: 20
- FWCI
- 10.34
- Type
- journal article
- Language
- en
- Open access
- green
- hdl.handle.net
- Licence
- cc-by-nc
- Locations
- Journal of The Electrochemical Society (publishedVersion)
- DSpace@MIT (Massachusetts Institute of Technology) (submittedVersion, cc-by-nc)
- Funders
- National Science Foundation (0819762)
- U.S. Department of Energy (DE‐FG02‐, FG02-05ER15728)
- Massachusetts Institute of Technology
- Materials Research Science and Engineering Center, Harvard University
- Division of Materials Research
- 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 oxidation, hydrogen evolution reaction, platinum electrocatalysts, polycrystalline platinum, alkaline electrolyte, exchange current density, Butler-Volmer kinetics, alkaline fuel cells, platinum loading, reaction mechanism
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