Cavity transport effects in generator-collector electrochemical analysis of nitrobenzene

G.E.M. Lewis, S.E.C. Dale, B. Kasprzyk-Hordern, A.T. Lubben, E.O. Barnes, R.G. Compton, F. Marken

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

Two types of generator-collector electrode systems, (i) a gold-gold interdigitated microband array and (ii) a gold-gold dual-plate microtrench, are compared for nitrobenzene electroanalysis in aerated aqueous 0.1 M NaOH. The complexity of the nitrobenzene reduction in conjunction with the presence of ambient levels of oxygen in the analysis solution provide a challenging problem in which feedback-amplified generator-collector steady state currents provide the analytical signal. In contrast to the more openly accessible geometry of the interdigitated array electrode, where the voltammetric response for nitrobenzene is less well-defined and signals drift, the voltammetric response for the cavity-like microtrench electrode is stable and readily detectable at 1 μM level. Both types of electrode show oxygen-enhanced low concentration collector current responses due to additional feedback via reaction intermediates. The observations are rationalised in terms of a "cavity transport coefficient" which is beneficial in the dual-plate microtrench, where oxygen interference effects are suppressed and the analytical signal is amplified and stabilised.
Original languageEnglish
Pages (from-to)18966-18973
Number of pages8
JournalPhysical Chemistry Chemical Physics
Volume16
Issue number35
Early online date5 Aug 2014
DOIs
Publication statusPublished - 21 Sep 2014

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nitrobenzenes
Gold
accumulators
generators
gold
cavities
Electrodes
electrodes
Oxygen
oxygen
Feedback
Reaction intermediates
reaction intermediates
low concentrations
transport properties
interference
Geometry
nitrobenzene
geometry

Cite this

Cavity transport effects in generator-collector electrochemical analysis of nitrobenzene. / Lewis, G.E.M.; Dale, S.E.C.; Kasprzyk-Hordern, B.; Lubben, A.T.; Barnes, E.O.; Compton, R.G.; Marken, F.

In: Physical Chemistry Chemical Physics , Vol. 16, No. 35, 21.09.2014, p. 18966-18973.

Research output: Contribution to journalArticle

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AB - Two types of generator-collector electrode systems, (i) a gold-gold interdigitated microband array and (ii) a gold-gold dual-plate microtrench, are compared for nitrobenzene electroanalysis in aerated aqueous 0.1 M NaOH. The complexity of the nitrobenzene reduction in conjunction with the presence of ambient levels of oxygen in the analysis solution provide a challenging problem in which feedback-amplified generator-collector steady state currents provide the analytical signal. In contrast to the more openly accessible geometry of the interdigitated array electrode, where the voltammetric response for nitrobenzene is less well-defined and signals drift, the voltammetric response for the cavity-like microtrench electrode is stable and readily detectable at 1 μM level. Both types of electrode show oxygen-enhanced low concentration collector current responses due to additional feedback via reaction intermediates. The observations are rationalised in terms of a "cavity transport coefficient" which is beneficial in the dual-plate microtrench, where oxygen interference effects are suppressed and the analytical signal is amplified and stabilised.

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