Dresden 2026 – wissenschaftliches Programm
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O: Fachverband Oberflächenphysik
O 97: Solid-liquid interfaces: Reactions and electrochemistry III
O 97.9: Vortrag
Freitag, 13. März 2026, 11:45–12:00, TRE/PHYS
An Analytical Description for Atomic Diffusion involved Peaks in Cyclic Voltammograms: the Reversible Place-Exchange on Pt(111) — Jon Bjarke Valbaek Mygind1, Francesc Valls Mascaró2, Gerard J. Verbiest3, and •Marcel J. Rost4 — 1Catalan Institute of Nanoscience and Nanotechnology, Campus UAB, Barcelona, Spain — 2Faculty of Physical Chemistry, University of Innsbruck, Innsbruck, Austria — 3Department of Precision and Microsystems Engineering, Delft University, Delft, The Netherlands — 4Huygens-Kamerlingh Onnes Laboratory, Leiden University, Leiden, The Netherlands
Cyclic voltammetry (CV) is one of the most powerful tools for the experimental investigation and characterization of electron transfer processes in electrochemistry. As the unique electrochemical fingerprint of a particular system is given by specific (current) peaks in the cyclic voltammogram, it is not surprising that great effort is done to understand, describe, and model these peaks. However, the underlying thermodynamic and kinetic processes make this a difficult task, especially when features in the fingerprint change with the applied CV sweep rate. Here we show, on the example of the reversible Place-Exchange peak, a precursor in the electrochemical oxidation of the Pt(111) surface, that a combination of a Frumkin isotherm followed by an Arrhenius (atomic) diffusion process delivers a rather good description. We present an analytical theory that fits all peaks of all CVs, measured with different sweep rates, with only six fit variables. These variables deliver hard quantitative thermodynamic values.
Keywords: cyclic voltammogram; modelling; Frumkin; Arrhenius; analytic description