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Dresden 2026 – wissenschaftliches Programm

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O: Fachverband Oberflächenphysik

O 97: Solid-liquid interfaces: Reactions and electrochemistry III

O 97.7: Vortrag

Freitag, 13. März 2026, 11:15–11:30, TRE/PHYS

Linking Water Structure to Proton-Coupled Electron Transfer at Metal Interfaces — •Julius Lonnes1,2, Nicolas G. Hörmann1, and Karsten Reuter11Fritz-Haber-Institut der MPG — 2Technische Universität München

Understanding the kinetics of interfacial electrochemical reactions is essential for optimizing technologies such as fuel cells and batteries. To this end, the interfacial water structure plays a key role in determining the effects of pH and electrolyte cations on reaction rates, yet the mechanistic link between water arrangement and reaction barriers remains unclear. By examining the acidic Volmer step on Pt(111) and tuning the hydrogen-bond network surrounding the proton, we uncover how interfacial solvation modulates electrochemical activation barriers. We find that proton stability at the metal-water interface strongly influences the barrier height, a relationship that can be rationalized with Hammond’s postulate:[1] variation in electrochemical potential shifts the transition state position along the reaction coordinate, altering its sensitivity to local solvation structure. We establish that interfacial solvation is a decisive factor in determining electrochemical activation energies, advancing fundamental understanding of proton-coupled electron transfer at charged interfaces.

[1] G.S. Hammond, J. Am. Chem. Soc. 77, 334 (1955).

Keywords: Interfacial Water Structures; Electrochemcial Barriers

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