Junqiao Lee

Oxygen reduction voltammetry on platinum macrodisk and screen-printed electrodes in ionic liquids: Reaction of the electrogenerated superoxide species with compounds used in the paste of Pt screen-printed electrodes?

Screen-printed electrodes (SPEs) are widely investigated as simple, three-electrode planar surfaces for electrochemical sensing applications, and may be ideal for gas sensing purposes when combined with non-volatile room temperature ionic liquids (RTILs). In this report the suitability of SPEs with RTIL solvents has been investigated for oxygen detection. Oxygen reduction has been studied on commercially available platinum SPEs in eight RTILs. Cyclic voltammetric wave shapes were found to be significantly different on Pt SPE surfaces compared to conventional solid Pt macroelectrodes, suggesting a possible reaction of the electrogenerated superoxide with the compounds that make up the ink/paste of the SPE surface. The only RTIL that did not show such drastically different voltammetry was one that contained a pyrrolidinium cation, suggesting a more chemically stable solvent environment compared to the other imidazolium and phosphonium cations studied. The analytical utility was then studied on four SPE surfaces (carbon, gold, platinum and silver) in two RTILs (one with a pyrrolidinium and one with an imidazolium cation) and linear responses were observed between current and % concentration in the range 10–100% O2. This suggests that SPEs may indeed be suitable for oxygen sensing in some RTILs, but significantly more pre-treatment of the surface is required to obtain reliable results. However, the reaction of superoxide with the SPE ink, together with a noticeable deterioration of the signal over time, suggests that this type of sensing platform may only be suitable for “single-use” oxygen sensing applications.

Achievement of Prolonged Oxygen Detection in Room-Temperature Ionic Liquids on Mechanically Polished Platinum Screen-Printed Electrodes

The demonstration of prolonged amperometric detection of oxygen in room-temperature ionic liquids (RTILs) was achieved by the use of mechanical polishing to activate platinum screen-printed electrodes (Pt-SPEs). The RTILs studied were 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][NTf2]) and N-butyl-N-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide ([C4mpyrr][NTf2]). It was found that voltammetry on polished Pt-SPEs exhibited less deterioration (in terms of voltammogram shapes, stability of peak currents, and appearance of contaminant peaks) from long-term consecutive cycling under 100% vol oxygen flow in both RTILs. The detection capability of these RTIL/Pt-SPE systems, initially subjected to long-term consecutive voltammetric cycling, was also investigated by cyclic voltammetry (CV) and long-term chronoamperometry (LTCA). Current versus concentration plots were linear on both unpolished and polished electrodes for 10-100% vol O2 (using CV) and 0.1-5% vol O2 (using LTCA). However, sensitivities and limits of detection (LODs) from CV were found to improve significantly on polished electrodes compared to unpolished electrodes, particularly in [C2mim][NTf2], but also moderately in [C4mpyrr][NTf2]. The lowest LODs (of ca. 0.1% vol O2) were found on polished SPEs using LTCA, with the most stable responses observed in [C4mpyrr][NTf2]. Calibration graphs could not be obtained on unpolished electrodes in both RTILs using LTCA. The results show that polishing markedly improves the analytical performances of Pt-SPEs for oxygen sensing in RTILs. The reusability of such disposable Pt-SPEs, after the surfaces had been experimentally fouled, was also demonstrated through the use of polishing. Mechanical polishing of Pt-SPE devices offers a viable approach to performance improvement for amperometric gas sensing.

Towards improving the robustness of electrochemical gas sensors: Impact of PMMA addition on the sensing of oxygen in an ionic liquid

The electrochemical reduction of oxygen (O2) has been studied on commercially-available integrated Pt thin-film electrodes (TFEs). Chemically reversible (but electrochemically quasi-reversible) cyclic voltammetry was observed in the room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][NTf2]), showing superior behaviour of TFEs compared to screen-printed electrodes for oxygen sensing. As a step towards the preparation of robust gas sensors, the RTIL was mechanically stabilised on the TFE surface by the addition of poly(methyl methacrylate) (PMMA). At a PMMA concentration in the RTIL of ca. 50% mass, electrolyte flow was not evident. O2 reduction peak currents were found to decrease systematically with increasing PMMA content, reflecting the higher viscosity of the electrolyte medium. Linear calibration graphs were obtained for 0–100% vol. oxygen at all PMMA–RTIL mixtures studied. The sensitivities decreased as [PMMA] increased, but the limits of detection were relatively unchanged. Mechanical stability of the sensors was tested in different orientations (flat, upside down, sideways) with both the neat RTIL and 50% mass electrolyte. Whilst the electrochemical responses were dramatically changed for the neat RTIL, the responses in the PMMA–RTIL mixture were independent of electrode orientation. Additionally, the oxygen response in the PMMA–RTIL mixture was less affected by atmospheric impurities and moisture, compared to the neat RTIL. This suggests that these low-cost miniaturised devices can successfully be used for oxygen sensing applications in field situations, especially where portability is essential.

Detection of 2,4,6-Trinitrotoluene Using a Miniaturized, Disposable Electrochemical Sensor with an Ionic Liquid Gel-Polymer Electrolyte Film

A new electrochemical method to detect and quantify the explosive compound 2,4,6-trinitrotoluene (TNT) in aqueous solutions is demonstrated. A disposable thin-film electrode modified with a droplet of a gel-polymer electrolyte (GPE) was immersed directly into samples of TNT at concentrations of 1-10 μg/mL. The GPE contained the hydrophobic room-temperature ionic liquid (RTIL) trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide ([P14,6,6,6][NTf2]) and the polymer poly(hexyl methacrylate). The RTIL acted to preconcentrate TNT into the GPE and provided ionic conductivity. The polymer provided both (i) sufficient viscosity to ensure mechanical stability of the GPE and (ii) strong hydrophobicity to minimize leaching of the RTIL. Square wave voltammetry was performed on the first reduction peak of TNT-preconcentrated samples (15 min soaking with mechanical stirring), with linear plots of peak current vs cumulative concentration of TNT, giving an averaged limit of detection of 0.37 μg/mL (aqueous phase concentration). Additionally, the voltammetry of the first reduction peak of TNT in [P14,6,6,6][NTf2] was unaffected by the presence of oxygen-in contrast to that observed in an imidazolium-based RTIL-providing excellent selectivity over oxygen in real environments. The sensor device was able to quickly and easily quantify TNT concentrations at typical ground water contamination levels. The low-cost and portability of the sensor device, along with the minimal amounts of GPE materials required, make this a viable platform for the onsite monitoring of explosives, which is currently a significant operational challenge.

Screen-Printed Graphite Electrodes as Low-Cost Devices for Oxygen Gas Detection in Room-Temperature Ionic Liquids

Screen-printed graphite electrodes (SPGEs) have been used for the first time as platforms to detect oxygen gas in room-temperature ionic liquids (RTILs). Up until now, carbon-based SPEs have shown inferior behaviour compared to platinum and gold SPEs for gas sensing with RTIL solvents. The electrochemical reduction of oxygen (O2) in a range of RTILs has therefore been explored on home-made SPGEs, and is compared to the behaviour on commercially-available carbon SPEs (C-SPEs). Six common RTILs are initially employed for O2 detection using cyclic voltammetry (CV), and two RTILs ([C2mim][NTf2] and [C4mim][PF6]) chosen for further detailed analytical studies. Long-term chronoamperometry (LTCA) was also performed to test the ability of the sensor surface for real-time gas monitoring. Both CV and LTCA gave linear calibration graphs—for CV in the 10–100% vol. range, and for LTCA in the 0.1–20% vol. range—on the SPGE. The responses on the SPGE were far superior to the commercial C-SPEs; more instability in the electrochemical responses were observed on the C-SPEs, together with some breaking-up or dissolution of the electrode surface materials. This study highlights that not all screen-printed ink formulations are compatible with RTIL solvents for longer-term electrochemical experiments, and that the choice of RTIL is also important. Overall, the low-cost SPGEs appear to be promising platforms for the detection of O2, particularly in [C4mim][PF6].

Electrochemical Reduction of 2,4-Dinitrotoluene in Room Temperature Ionic Liquids: A Mechanistic Investigation*

The reduction mechanism of 2,4-dinitrotoluene (DNT) has been studied in eight room temperature ionic liquids (RTILs) using cyclic voltammetry (CV), square wave voltammetry (SWV), chronoamperometry, and digital simulation. Two distinctive peaks are observed in the voltammetry, corresponding to the stepwise reduction of the two nitro groups on the aromatic ring. Diffusion coefficients (D) and electron counts (n) were calculated from chronoamperometric transients, revealing an electron count of one in most RTILs, and a linear relationship between D and the inverse of viscosity. Focusing on the first reduction only, the peak appears to be chemically reversible at low concentrations. However, as the concentration increases, the current of the reverse peak diminishes, suggesting that one or more chemical steps occur after the electrochemical step. The results from digital simulation of the CVs in one of the RTILs reveal that the most likely mechanism involves a deprotonation of the methyl group of a parent DNT molecule by the electrogenerated radical anion and/or a dimerisation of two electrogenerated radical anions. Elucidation of the reduction mechanism of DNT (and other explosives) is vital if electrochemical techniques are to be employed to detect these types of compounds in the field.