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Tichter, Tim ; Schneider, Jonathan ; Roth, Christina:
Finite Heterogeneous Rate Constants for the Electrochemical Oxidation of VO²⁺ at Glassy Carbon Electrodes.
In: Frontiers in Energy Research.
Bd. 8
(2020)
.
- 155.
ISSN 2296-598X
DOI: https://doi.org/10.3389/fenrg.2020.00155
Abstract
The electrochemical oxidation of VO2+ at planar glassy carbon electrodes is investigated via stationary and rotating linear sweep voltammetry as well as via chronoamperometry. It is demonstrated that introducing finite kinetic rate constants into the Butler-Volmer equation captures the experimentally observed concentration dependence of the ordinate intercept in Koutecký-Levich plots that cannot be explained by using the classical model. This new concept leads to a three-term Koutecký-Levich equation considering mass transport limitations, Butler-Volmer kinetics, as well as finite heterogeneous kinetics simultaneously. Based on these findings it is pointed out that stationary linear sweep voltammetry followed by an irreversible Randles-Ševčík analysis is not sufficient for deducing the electrode kinetics of the VO2+-oxidation. In contrast, it is verified experimentally and theoretically that a Tafel analysis will still provide reasonable values of k0 = 1.35 · 10−5 cm/s and α = 0.38, respectively. Finally, it is shown that introducing the concept of finite heterogeneous kinetics into the theory of stationary linear sweep voltammetry also explains the failure of the irreversible Randles-Ševčík relation leading to an extension of the classical model and providing insight into the electrochemical oxidation reaction of VO2+.
Weitere Angaben
| Publikationsform: | Artikel in einer Zeitschrift |
|---|---|
| Begutachteter Beitrag: | Ja |
| Institutionen der Universität: | Fakultäten > Fakultät für Ingenieurwissenschaften > Lehrstuhl Werkstoffverfahrenstechnik > Lehrstuhl Werkstoffverfahrenstechnik - Univ.-Prof. Dr. Christina Roth Fakultäten Fakultäten > Fakultät für Ingenieurwissenschaften Fakultäten > Fakultät für Ingenieurwissenschaften > Lehrstuhl Werkstoffverfahrenstechnik |
| Titel an der UBT entstanden: | Nein |
| Themengebiete aus DDC: | 500 Naturwissenschaften und Mathematik > 540 Chemie 600 Technik, Medizin, angewandte Wissenschaften > 620 Ingenieurwissenschaften |
| Eingestellt am: | 22 Apr 2021 07:30 |
| Letzte Änderung: | 14 Jun 2023 11:42 |
| URI: | https://eref.uni-bayreuth.de/id/eprint/64868 |