Stripping away ion hydration shells in electrical double-layer formation: Water networks matter.

Alfarano, Serena R; Pezzotti, Simone; Stein, Christopher J; Lin, Zhou; Sebastiani, Federico; Funke, Sarah; Hoberg, Claudius; Kolling, Inga et al. · Proc Natl Acad Sci U S A · 2021

basic_science · Level V

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Abstract

The double layer at the solid/electrolyte interface is a key concept in electrochemistry. Here, we present an experimental study combined with simulations, which provides a molecular picture of the double-layer formation under applied voltage. By THz spectroscopy we are able to follow the stripping away of the cation/anion hydration shells for an NaCl electrolyte at the Au surface when decreasing/increasing the bias potential. While Na<sup>+</sup> is attracted toward the electrode at the smallest applied negative potentials, stripping of the Cl<sup>-</sup> hydration shell is observed only at higher potential values. These phenomena are directly measured by THz spectroscopy with ultrabright synchrotron light as a source and rationalized by accompanying molecular dynamics simulations and electronic-structure calculations.