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2,4-Toluene diisocyanate detection in liquid and gas environments through electrochemical oxidation in an ionic liquid.

ABSTRACT: The electrochemical oxidation of 2,4-toluene diisocyanate (2,4-TDI) in an ionic liquid (IL) has been systematically characterized to determine plausible electrochemical and chemical reaction mechanisms and to define the optimal detection methods for such a highly significant analyte. It has been found that the use of an IL as the electrolyte allows the oxidation of 2,4-TDI to occur at a less positive anodic potential with no side reactions as compared to traditional acetonitrile based electrolytes. UV-Vis, FT-IR, cyclic voltammetry and Electrochemical Impedance Spectroscopy (EIS) studies have revealed the unique mechanisms of dimerization of 2,4-TDI at the electrode interface by self-addition reactions, which can be utilized to improve the selectivity of detection. The study of 2,4-TDI redox chemistry further facilitates the development of a robust amperometric sensing methodology by selecting a hydrophobic IL ([C4mpy][NTf2]) and by restricting the potential window to only include the oxidation process. Thus, this innovative electrochemical sensor is capable of avoiding the two most ubiquitous interferents in ambient conditions (i.e. humidity and oxygen), thereby enhancing the sensor performance and reliability for real world applications. The method was established to detect 2,4-TDI in both liquid and gas phases. The limits of detection (LOD) values were 130.2 ppm and 0.7862 ppm, respectively, for the two phases, and are comparable to the safety standards reported by NIOSH. The as-developed 2.4-TDI amperometric sensor exhibits a sensitivity of 1.939 ?A ppm(-1). Moreover, due to the simplicity of design and the use of an IL both as a solvent and non-volatile electrolyte, the sensor has the potential to be miniaturized for smart sensing protocols in distributed sensor applications.

SUBMITTER: Lin L

PROVIDER: S-EPMC4756716 | biostudies-literature | 2016 Feb

REPOSITORIES: biostudies-literature

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2,4-Toluene diisocyanate detection in liquid and gas environments through electrochemical oxidation in an ionic liquid.

Lin Lu L Rehman Abdul A Chi Xiaowei X Zeng Xiangqun X

The Analyst 20160201 4

The electrochemical oxidation of 2,4-toluene diisocyanate (2,4-TDI) in an ionic liquid (IL) has been systematically characterized to determine plausible electrochemical and chemical reaction mechanisms and to define the optimal detection methods for such a highly significant analyte. It has been found that the use of an IL as the electrolyte allows the oxidation of 2,4-TDI to occur at a less positive anodic potential with no side reactions as compared to traditional acetonitrile based electrolyt ...[more]

PMID: 26763507

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Project description:Electrochemical amperometric sensors require a constant or varying potential at the working electrode that drives redox reactions of the analyte for detection. The interfacial redox reaction(s) can result in the formation of new chemical products that could change the initial condition of the electrode/electrolyte interface. If the products are not inert and/or cannot be removed from the system such that the initial condition of the electrode/electrolyte interface cannot be restored, the sensor signal baseline would consequently drift, which is problematic for the continuous and real-time sensors. By setting the electrode potential with the periodical ON-OFF mode, electrolysis can be forestalled during the off mode which can minimize the sensor signal baseline drift and reduce the power consumption of the sensor. However, it is known that the relaxation of the structure in the electrical double layer at the ionic liquid/electrode interface to the steps of the electrode potential is slow. This work characterized the electrode/electrolyte interfacial relaxation process of an ionic liquid based electrochemical gas (IL-EG) sensor by performing multiple potential step experiments in which the potential is stepped from an open circuit potential (OCP) to the amperometric sensing potential at various frequencies with different time periods. Our results showed that by shortening the sensing period as well as extending the idle period (i.e., enlarge the ratio of idle period versus sensing period) of the potential step experiments, the electrode/electrolyte interface is prone to relax to its original state, and thus reduces the baseline drift. Additionally, the high viscosity of the ionic liquids is beneficial for electrochemical regeneration via the implementation of a conditioning step at zero volts at the electrode/electrolyte. By setting the working electrode at zero volts instead of OCP, our results showed that it could further minimize the baseline drift, enhance the sensing signal stability, and extend the functioning lifetime of a continuous IL-EG oxygen sensor.

Dataset Information

2,4-Toluene diisocyanate detection in liquid and gas environments through electrochemical oxidation in an ionic liquid.

Publications

2,4-Toluene diisocyanate detection in liquid and gas environments through electrochemical oxidation in an ionic liquid.

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