Publication: Quantitative analysis of the electrochemical performance of multi-redox molecular electrocatalysts. A mechanistic study of chlorate electrocatalytic reduction in presence of a molybdenium polyoxometalate
Authors
González Sánchez, Joaquín ; Gillén, Esteban ; Laborda, Eduardo ; Molina, Angela
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Publisher
Elsevier
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DOI
https://doi.org/10.1016/j.jcat.2022.06.038
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info:eu-repo/semantics/article
Description
© 2022 The Authors. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/
This document is the Published Manuscript version of a Published Work that appeared in final form in Journal of Catalysis. To access the final edited and published work see https://doi.org/10.1016/j.jcat.2022.06.038
Abstract
The quantification of the performance efficiency of a given molecular electrocatalyst versus a particular substrate of interest requires the determination of the rate constants of the catalytic steps taking place in the overall reaction pathway. In this paper, a theoretical model is presented for the quantitative analysis of the voltammetric response of multi-redox catalysts, that is, a molecular species with different redox states that can act in different electrocatalytic forms as a function of the applied potential. The rigorous theoretical model presented incorporates mass transport effects and it is applicable to disc electrodes of any size. As a model system, the electro-reduction of the anion chlorate by the polyoxometalate [PMo12O40]3- (POM) is analysed at gold electrodes. The overall process implies ten charge transfer steps and three different two-electron catalytic processes, the formal potentials and rate constants of which are accurately determined, respectively. The logarithm of the rate constants for the three catalytic steps follows a linear relationship with the average formal potentials of the two-electron charge transfer processes. A comparison with previous efforts devoted to the characterisation of electrocatalytic responses is also carried out, pointing out the advantages of a rigorous solution for this problem.
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Citation
Journal of Catalysis, 2022, Vol. 413, pp. 467-477
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