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Finite Heterogeneous Rate Constants for the Electrochemical Oxidation of VO²⁺ at Glassy Carbon Electrodes

Title data

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. Vol. 8 (2020) .
ISSN 2296-598X
DOI: https://doi.org/10.3389/fenrg.2020.00155

Abstract in another language

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+.

Further data

Item Type: Article in a journal
Refereed: Yes
Institutions of the University: Faculties > Faculty of Engineering Science > Chair Electrochemical Process Engineering > Chair Electrochemical Process Engineering - Univ.-Prof. Dr. Christina Roth
Result of work at the UBT: No
DDC Subjects: 500 Science > 540 Chemistry
600 Technology, medicine, applied sciences > 620 Engineering
Date Deposited: 22 Apr 2021 07:30
Last Modified: 22 Apr 2021 07:30
URI: https://eref.uni-bayreuth.de/id/eprint/64868