Insights into solvent and surface charge effects on Volmer step kinetics on Pt (111)

Wilson, Jon C.; Caratzoulas, Stavros; Vlachos, Dionisios G.; Yan, Yushan

doi:10.1038/s41467-023-37935-6

Title: Insights into solvent and surface charge effects on Volmer step kinetics on Pt (111)

Journal Article · 24 April 2023 · Nature Communications

DOI: https://doi.org/10.1038/s41467-023-37935-6 · OSTI ID:1971395

Wilson, Jon C.;

;

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.

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Sponsoring Organization:: USDOE

OSTI ID:: 1971395

Alternate ID(s):: OSTI ID: 2419580

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 14; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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