Insights into solvent and surface charge effects on Volmer step kinetics on Pt (111)
Date
2023-04-25
Journal Title
Journal ISSN
Volume Title
Publisher
Nature Communications
Abstract
The mechanism of pH-dependent hydrogen oxidation and evolution kinetics is still a matter of significant debate. To make progress, we study the Volmer step kinetics on platinum (111) using classical molecular dynamics simulations with an embedded Anderson-Newns Hamiltonian for the redox process and constant potential electrodes. We investigate how negative electrode electrostatic potential affects Volmer step kinetics. We find that the redox solvent reorganization energy is insensitive to changes in interfacial field strength. The negatively charged surface attracts adsorbed H as well as H+, increasing hydrogen binding energy, but also trapping H+ in the double layer. While more negative electrostatic potential in the double layer accelerates the oxidation charge transfer, it becomes difficult for the proton to move to the bulk. Conversely, reduction becomes more difficult because the transition state occurs farther from equilibrium solvation polarization. Our results help to clarify how the charged surface plays a role in hydrogen electrocatalysis kinetics.
Description
The version of record of this article, first published in Nature Communications, is available online at Publisher’s website: https://doi.org/10.1038/s41467-023-37935-6. © The Author(s) 2023
Keywords
catalytic mechanisms, electrochemistry, energy, reaction mechanisms
Citation
Wilson, J.C., Caratzoulas, S., Vlachos, D.G. et al. Insights into solvent and surface charge effects on Volmer step kinetics on Pt (111). Nat Commun 14, 2384 (2023). https://doi.org/10.1038/s41467-023-37935-6