Dynamics of Redox Processes
in Ionic Liquids and Their
Interplay for Discriminative Electrochemical Sensing
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Abstract
Motivated by the use of ionic liquids (ILs) as green
replacers
of traditional electrolytes, a mechanistic study has been systematically
conducted to comprehend various design principles responsible for
electrochemical profiling of redox-active species in ILs. The full
spectrum of properties associated with ILs is exploited to assess
the viability of this platform, thus revealing the correlation between
the redox properties and the physiochemical parameters of the species
involved. This includes the evaluation of (1) the variation of redox
responses toward analytes with similar molecular structures or functionalities
of ILs, (2) the influence in terms of physical criteria of the system
such as viscosity and conductivity as well as chemical structure of
ILs, and (3) the sustainability in harsh conditions (high temperature
or humidity) and interferences. The principle is exemplified via trinitrotoluene
(TNT) and dinitrotoluene (DNT) with inherent redox activity as analytes
and IL membranes as solvents and electrolytes using glassy carbon
(GC) electrodes. A discrete response pattern is generated that is
analyzed through linear discriminant analysis (LDA) leading to 100%
classification accuracy even for the mixture of analytes. Quantitative
analysis through square wave voltammetry (SWV) gave rise to the detection
limits in liquid phase of 190 and 230 nM for TNT and DNT, respectively,
with a linear range up to 100 μM. Gas-phase analysis shows strong
redox signals for the estimated concentrations of 0.27 and 2.05 ppm
in the gas phase for TNT and DNT, respectively, highlighting that
ILs adopt a role as a preconcentrator to add on sensitivity with enhanced
selectivity coming from their physiochemical diversity, thus addressing
the major concerns usually referred to most sensor systems