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Water Structure and Mechanisms of Proton Discharge on Platinum Electrodes: Empirical Valence Bond Molecular Dynamics Trajectory Studies

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Abstract

We present a comparative analysis of molecular dynamics trajectory studies of the influence of surface charge, ion strength, and ion adsorption on the interfacial water structure and the possible pathways of proton transport and discharge on negatively charged platinum(111) electrodes. The model used is a reactive force field based on a nine-state empirical valence bond model. It incorporates both proton transfer between water molecules and simultaneous electron and proton transfer to the metal (discharge). The interfacial water polarization is the result of the competition between the electrical field influence of the smooth surface charge and the point-like local charges of adsorbed positive or negative ions, which leads to variations of the prevalent proton discharge pathways depending on system composition.

In trajectory calculations of proton adsorption and discharge from aqueous solutions onto charged platinum electrodes, the presence of electrolytes in the adsorbate layer influences proton discharge mechanisms via changes in water orientation and via exclusion of discharge sites through repulsive cation-proton interactions.

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Acknowledgements

This work was performed with financial support by DFG within the framework of the DFG Research Unit 1376 “Elementary reaction steps in electrocatalysis: Theory meets Experiment,” for which we thank the DFG. ES is also grateful for support by the Cluster of Excellence RESOLV (EXC1069) funded by the Deutsche Forschungsgemeinschaft. Computations were in part performed at the UDE Cray computer operated by CCSS and ZIM.

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  1. Faculty of Chemistry, Duisburg-Essen University, 45117, Essen, Germany

    Johannes Wiebe

  2. Faculty of Chemistry and Center for Computational Sciences and Simulation (CCSS), Universität Duisburg-Essen, 45117, Essen, Germany

    Eckhard Spohr

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  1. Johannes Wiebe
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Correspondence to Johannes Wiebe or Eckhard Spohr.

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Wiebe, J., Spohr, E. Water Structure and Mechanisms of Proton Discharge on Platinum Electrodes: Empirical Valence Bond Molecular Dynamics Trajectory Studies. Electrocatalysis 8, 637–646 (2017). https://doi.org/10.1007/s12678-017-0398-2

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