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Modelling electrochemical modulation of ion release in thin-layer samples
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry.
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Applied Physical Chemistry.ORCID iD: 0000-0001-7941-2312
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry.
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Applied Physical Chemistry.ORCID iD: 0000-0002-3858-8466
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2021 (English)In: JOURNAL OF ELECTROANALYTICAL CHEMISTRY, ISSN 1572-6657, Vol. 903, p. 115851-, article id 115851Article in journal (Refereed) Published
Abstract [en]

In this work, we present a model based on the finite element approach to describe the electrochemically controlled release of ions from a redox-active film into a sample confined to a thin-layer spatial domain. The model includes the effect of interfacial charge transfer kinetics and 1D-diffusion treatment for an electron transfer-ion transfer (ET-IT) coupled reaction. More in detail, the oxidation of the redox-active film (ET) involves an ion release to an aqueous phase (IT). The dynamic concentration of the released ion is calculated when the ET-IT reaction proceeds under potentiostatic control, and the effect of the thickness of each phase (i.e., film or aqueous) on the diffusion profile is analyzed. The model is experimentally validated for the particular case in which oxidation of a thin film of polyaniline (PANI, 10 mu m in thickness) is linked to the release of protons from the film into an electrolyte solution. The proton release produces certain pH changes in the electrolyte that are monitored by a pH sensor located at 330 mu m from the PANI film. The charge associated with the proton release is related to the dynamic concentration of protons in the electrolyte through pH-coulograms that agree with the theoretical predictions. Overall, the model can reproduce the general behavior of the experimental proton pump and provides key insights into the functioning mechanism of electrochemical systems where redox and ion transfer reactions are coupled.

Place, publisher, year, edition, pages
Elsevier BV , 2021. Vol. 903, p. 115851-, article id 115851
Keywords [en]
Thin-layer titration, Polyaniline film, Ion-transfer, Charge transfer, Modelling, Ion pump, Finite element
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URN: urn:nbn:se:kth:diva-306857DOI: 10.1016/j.jelechem.2021.115851ISI: 000732768700002Scopus ID: 2-s2.0-85119351594OAI: oai:DiVA.org:kth-306857DiVA, id: diva2:1624603
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QC 20220104

Available from: 2022-01-04 Created: 2022-01-04 Last updated: 2022-06-25Bibliographically approved

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Molina Osorio, AndresWiorek, AlexanderHussain, GhulamCuartero, MariaCrespo, Gaston A.

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