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Pulsed chronopotentiometric membrane electrodes based on plasticized poly(vinyl chloride) with covalently bound ferrocene functionalities as solid contact transducer

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Published in Pure and Applied Chemistry. 2012, vol. 84, no. 10, p. 2045-2054
Abstract Ion-selective membrane materials based on poly(vinyl chloride) (PVC)-containing covalently attached redox-active ferrocene (Fc) groups are characterized here as all-solid-state pulsed voltammetric ion sensors. The redox capacity of the membrane increases 7-fold with a doubling of the Fc content and 3-fold with the addition of 10 wt % of the lipophilic electrolyte ETH 500, tetradodecylammonium tetrakis(4-chlorophenyl)borate. This salt improves the ionic conductivity of the membrane and appears to make the Fc groups electrochemically more accessible. A too high content of the two, on the other hand, was found to cause undesired sensitivity to redox-active species present in the sample solution. Dilution of the membrane with a plasticizer eliminated this redox sensitivity while preserving its high redox capacity. A practical application of the designed electrodes in electrochemical analysis was demonstrated with a multi-pulse protocol that includes a current-controlled ion uptake pulse, followed by an open-circuit potential (OCP) measurement and a regeneration pulse. Potentiometric calibration curves obtained with this protocol exhibited a linear response with near-Nernstian slopes for acetate, nitrate, chloride, and perchlorate ions with the selectivity expected for an ion-exchanging membrane.
Keywords Analytical chemistryClick chemistryElectrochemistryIon-selective electrodesLiquid–liquid interfacesMembranesModified poly(vinyl chloride)Solid-state electrodes
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PAWLAK, Marcin, GRYGOLOWICZ-PAWLAK, Ewa, BAKKER, Eric. Pulsed chronopotentiometric membrane electrodes based on plasticized poly(vinyl chloride) with covalently bound ferrocene functionalities as solid contact transducer. In: Pure and Applied Chemistry, 2012, vol. 84, n° 10, p. 2045-2054. doi: 10.1351/PAC-CON-11-09-23 https://archive-ouverte.unige.ch/unige:144408

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Deposited on : 2020-11-10

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