Thomas Ludwig, Stanford University

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The electrolyte is a critical part of electrochemical systems. A systematic understanding of electrolyte effects in electrochemical catalysis would facilitate the rational design of the electrolyte as an integral part of optimizing important electrochemical processes.

Experimentally, it has been demonstrated that many properties of the electrolyte significantly affect the selectivity and activity of electrocatalytic processes.

Accurate theoretical study of metal-electrolyte interfaces has historically been challenging for several reasons, as it requires simultaneously including detailed electronic structure and chemisorption effects from the metal and also many intermolecular interactions and long-range electrostatic effects from the electrolyte, all of which should, in principle, be sampled over an ensemble of realistic configurations.

We investigate electrolyte structure and solvent-adsorbate interactions with various relevant reactive intermediates on metal surfaces using density functional theory. We find that adsorbates have significant and specific effects on the local electrolyte structure and that accurate sampling of ion and solvent configurations is highly important in accurately modeling electrochemical reactions. This work is a step toward the important goal of understanding and ultimately engineering the electrolyte and the electrochemical interface for optimal performance in efficient electrochemical processes.

Abstract Author(s): Thomas Ludwig, Karen Chan, Jens K. Nørskov