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 editorsZhen, 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 seriesPrecision Chemistry

eISSN2771-9316

Publication year2025

Publication date08/01/2025

VolumeEarly online

PublisherAmerican Chemical Society (ACS)

Publication countryUnited States

Publication languageEnglish

DOIhttps://doi.org/10.1021/prechem.4c00081

Publication open accessOpenly available

Publication channel open accessOpen 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.


Keywordschemical reactionshydrogenelectrocatalysispHsurface chemistryelectrochemistry

Free keywordshydrogen evolution reaction; Au(111) electrode; pH effect; rate constants; EDL effects


Contributing organizations


Ministry reportingYes

VIRTA submission year2025


Last updated on 2025-25-01 at 20:05