Solid contact ion-selective electrodes with a well-controlled Co(II)/Co(III) redox buffer layer

Xu U. Zou, Jia H. Cheong, Brandon J. Taitt, Philippe Bühlmann

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Solid contact ion-selective electrodes (ISEs) typically have an intermediate layer between the ion-selective membrane and the underlying solid electron conductor that is designed to reduce the irreproducibility and instability of the measured electromotive force (emf). Nevertheless, the electrode-to-electrode reproducibility of the emf of current solid contact ISEs is widely considered to be unsatisfactory. To address this problem, we report here a new method of constructing this intermediate layer based on the lipophilic redox buffer consisting of the Co(III) and Co(II) complexes of 1,10-phenanthroline ([Co(phen)3]3+/2+) paired with tetrakis(pentafluorophenyl)borate as counterion. The resulting electrodes exhibit emf values with an electrode-to-electrode standard deviation as low as 1.7 mV after conditioning of freshly prepared electrodes for 1 h. While many prior examples of solid contact ISEs also used intermediate layers that contained redox active species, the selection of a balanced ratio of the reduced and oxidized species has typically been difficult and was often ignored, contributing to the emf irreproducibility. The ease of the control of the [Co(phen)3]3+/[Co(phen)3]2+ ratio explains the high emf reproducibility, as confirmed by the emf decrease of 58 mV per 10-fold increase in the ratio of the reduced and oxidized redox buffer species. Use of a gold electrode modified with a self-assembled 1-hexanethiol monolayer as underlying electron conductor suppresses the formation of a water layer and results in an electrode-to-electrode standard deviation of E of 1.0 mV after 2 weeks of exposure to KCl solution.

Original languageEnglish (US)
Pages (from-to)9350-9355
Number of pages6
JournalAnalytical Chemistry
Issue number19
StatePublished - Oct 1 2013


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