A1 Journal article (refereed)
Disentangling Multiple pH-Dependent Factors on the Hydrogen Evolution Reaction at Au(111) (2025)
Zhen, E.-F., Liu, B.-Y., Zhang, M.-K., Zhang, L., Zhang, C.-Y., Cai, J., Melander, M. M., Huang, J., & Chen, Y.-X. (2025). Disentangling Multiple pH-Dependent Factors on the Hydrogen Evolution Reaction at Au(111). Precision Chemistry, Early online. https://doi.org/10.1021/prechem.4c00081
JYU authors or editors
Publication details
All authors or editors: Zhen, Er-Fei; Liu, Bing-Yu; Zhang, Meng-Ke; Zhang, Lu−Lu; Zhang, Chen-Yu; Cai, Jun; Melander, Marko M.; Huang, Jun; Chen, Yan-Xia
Journal or series: Precision Chemistry
eISSN: 2771-9316
Publication year: 2025
Publication date: 08/01/2025
Volume: Early online
Publisher: American Chemical Society (ACS)
Publication country: United States
Publication language: English
DOI: https://doi.org/10.1021/prechem.4c00081
Publication open access: Openly available
Publication channel open access: Open Access channel
Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/99364
Abstract
Understanding how the electrolyte pH affects electrocatalytic activity is a topic of crucial importance in a large variety of systems. However, unraveling the origin of the pH effects is complicated often by the fact that both the reaction driving forces and reactant concentrations in the electric double layer (EDL) change simultaneously with the pH value. Herein, we employ the hydrogen evolution reaction (HER) at Au(111)-aqueous solution interfaces as a model system to disentangle different pH-dependent factors. In 0.1 M NaOH, the HER current density at Au(111) in the potential range of −0.4 V < ERHE < 0 V is up to 60 times smaller than that in 0.1 M HClO4. A reaction model with proper consideration of the local reaction conditions within the EDL is developed. After correcting for the EDL effects, the rate constant for HER is only weakly pH-dependent. Our analysis unambiguously reveals that the observed pH effects are mainly due to the pH-dependent reorganization free energy, which depends on the electrostatic potential and the local reaction conditions within the EDL. Possible origins of the pH and temperature dependence of the activation energy and the electron transfer coefficients are discussed. This work suggests that factors influencing the intrinsic pH-dependent kinetics are easier to understand after proper corrections of EDL effects.
Keywords: chemical reactions; hydrogen; electrocatalysis; pH; surface chemistry; electrochemistry
Free keywords: hydrogen evolution reaction; Au(111) electrode; pH effect; rate constants; EDL effects
Contributing organizations
Ministry reporting: Yes
VIRTA submission year: 2025
- Physical Chemistry (Department of Chemistry CHEM) KEF
- School of Resource Wisdom (University of Jyväskylä JYU) JYU.Wisdom
- Nanoscience Center (Department of Physics PHYS, JYFL) (Faculty of Mathematics and Science) (Department of Chemistry CHEM) (Department of Biological and Environmental Science BIOENV) NSC
- Chemistry (Department of Chemistry CHEM) KEM