All solid state chronopotentiometric ion-selective electrodes based on ferrocene functionalized PVC

Zdenka Jarolimova; Gaston Adrian Crespo; M G Afshar; M Pawlak; Eric Bakker

doi:10.1016/j.jelechem.2013.10.011

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All solid state chronopotentiometric ion-selective electrodes based on ferrocene functionalized PVC

Journal article

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All solid state chronopotentiometric ion-selective electrodes based on ferrocene functionalized PVC

Zdenka Jarolimova, Gaston Adrian Crespo, M G Afshar, M Pawlak and Eric Bakker

Journal of Electroanalytical Chemistry, Vol.709, pp.118-125

2013

DOI: https://doi.org/10.1016/j.jelechem.2013.10.011

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Abstract

Analytical Chemistry

chronopotentiometry

permselective membranes

ion-selective membranes

solid contact transducer

ferrocene

An all solid contact ion-selective electrode based on poly(vinyl chloride) covalently modified with ferrocene moieties allows one to operate the membrane in a chronopotentiometric sensing mode. The membrane is considered as initially non-perm-selective towards anions, and an applied anodic current provokes a defined anion flux in direction of the membrane. With this protocol, a variety of anions can be depleted at the membrane surface. Since this model system does not yet contain an ionophore, their order of preference follows the expected Hofmeister selectivity sequence. The all solid-state configuration tolerates an imposed current density of 1.4 μA mm-2, which translates into an upper detection limit of ca. 1.2 mM. Higher current densities of up to 31.2 μA mm-2 are possible with addition of freely dissolved alkyl ferrocene derivative for an expected upper detection limit of 17.0 mM. Numerical simulations are performed in order to establish the fundamental basis of the mechanism that takes place in this all solid-state membrane electrode. The oxidation of bound Fc and the ion-transfer process are considered in the simulation. In view of developing an analytical sensor, different anions are tested. A linear range of two orders of magnitude from 0.01 to 1 mM is found. The membranes are evaluated over several days, displaying practically the same slopes and intercepts, with a RSD of less than 2%. Electrochemical limitations of free Fc and bound Fc are critical evaluated. This approach should allow one to develop a new family of solid-state chronopotentiometric ion sensors that require relatively high current densities.

Details

Title: All solid state chronopotentiometric ion-selective electrodes based on ferrocene functionalized PVC
Authors: Zdenka Jarolimova (Author) - University of Geneva, Switzerland
Gaston Adrian Crespo (Author) - University of Geneva, Switzerland
M G Afshar (Author) - University of Geneva, Switzerland
M Pawlak (Author) - University of Geneva, Switzerland
Eric Bakker (Author) - University of Geneva, Switzerland
Publication details: Journal of Electroanalytical Chemistry, Vol.709, pp.118-125
Publisher: Elsevier S.A.
Date published: 2013
DOI: 10.1016/j.jelechem.2013.10.011
ISSN: 1572-6657; 1572-6657
Organisation Unit: University of the Sunshine Coast, Queensland
Language: English
Record Identifier: 99449010302621
Output Type: Journal article

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Web Of Science research areas: Chemistry, Analytical; Electrochemistry