Elucidating Hydrogen Oxidation/Evolution Kinetics in Base and Acid by Enhanced Activities at the Optimized Pt Shell Thickness on the Ru Core
Open accessAbstract
Hydrogen oxidation and evolution on Pt in acid are facile processes, while in alkaline electrolytes, they are 2 orders of magnitude slower. Thus, developing catalysts that are more active than Pt for these two reactions is important for advancing the performance of anion exchange membrane fuel cells and water electrolyzers. Herein, we detail a 4-fold enhancement of Pt mass activity that we achieved using single-crystalline Ru@Pt core–shell nanoparticles with two-monolayer-thick Pt shells, which doubles the activity on Pt–Ru alloy nanocatalysts. For Pt specific activity, the two- and one-monolayer-thick Pt shells exhibited enhancement factors of 3.1 and 2.3, respectively, compared to the Pt nanocatalysts in base, differing considerably from the values of 1 and 0.4, respectively, in acid. To explain such behavior and the orders of magnitude difference in activity on going from acid to base, we performed kinetic analyses of polarization curves over a wide range of potential from −250 to 250 mV using the dual-pathway kinetic equation. From acid to base, the activation free energies increase the most for the Volmer reaction, resulting in a switch of the rate-determining step from the Tafel to the Volmer reaction, and a shift to a weaker optimal hydrogen binding energy. The much higher activation barrier for the Volmer reaction in base than in acid is ascribed to one or both of the two catalyst-insensitive factors: slower transport of OH– than H+ in water and a stronger O–H bond in water molecules (HO–H) than in hydrated protons (H2O–H+).
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Increased HBE on Pt at high pH leads to much more sluggish HOR kinetics in alkaline media.
“The increased HBE on Pt at a high pH leads to the much more sluggish HOR kinetics in alkaline media [22,23].”
From Lamellar platinum–rhodium aerogels with superior electrocatalytic performance for both hydrogen oxidation and evolution reaction in alkaline environment (2019) · cites this paper as [22]
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- Authors
- Elbert, K., Hu, J., Ma, Z., Zhang, Y., Chen, G., An, W., Liu, P., Isaacs, H. S., Adzic, R. R., & Wang, J. X.
- Affiliations
- Brookhaven National Laboratory (US)
- Brookhaven National Laboratory , , , ,
- Corresponding author
- Wang, Jia X.
- Venue
- ACS Catalysis
- Publisher
- American Chemical Society (ACS)
- Published
- 2015-10-05
- Volume
- 5
- Issue
- 11
- Pages
- 6764-6772
- ISSN
- 2155-5435 (ISSN-L)
- OpenAlex
- W2274643055
- Cited by
- 241
- References
- 4
- Citations by year
- 2026: 8 · 2025: 13 · 2024: 23 · 2023: 22 · 2022: 31 · 2021: 21 · 2020: 35 · 2019: 30 · 2018: 22 · 2017: 25 · 2016: 11
- FWCI
- 5.72
- Type
- journal article
- Language
- en
- Open access
- hybrid
- doi.org
- Locations
- ACS Catalysis (publishedVersion, other-oa)
- OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information) (submittedVersion)
- Funders
- U.S. Department of Energy (DE-SC0012704)
- National Natural Science Foundation of China (21336003)
- Chinese Academy of Sciences (2015265)
- Ministry of Science and Technology of the People's Republic of China (2014CB239703)
- China Scholarship Council (NA)
- 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 › Catalytic Processes in Materials Science
- Keywords
- hydrogen oxidation, hydrogen evolution reaction, alkaline electrocatalysis, acidic electrocatalysis, Volmer reaction, activation free energy, hydrogen binding energy, anion exchange membrane fuel cells, water electrolyzer, polarization curves
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