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. © 2016 American Chemical Society

Synthesis, photophysical and electrochemical investigation of dinuclear tetrazolato-bridged rhenium complexes

Starting from anionic tetrazole-based ligands, namely 5-(4’-cyanophenyl)tetrazolate and 5-(4’-pyridyl)tetrazolate, mononuclear and dinuclear complexes of fac-[Re(CO)3(phen)]+ (phen = 1,10-phenanthroline) were prepared and characterized. For the mononuclear complexes, regioselective coordination of the metal fragments on the negatively charged tetrazolato ring is exclusively obtained. Coordination to the benzonitrile and pyridine groups was achieved by previous alkylation of the tetrazole ring. Dinuclear complexes were obtained by treatment of the corresponding mononuclear tetrazole-bound complexes with fac-[Re(CO)3(phen)(THF)]+. The second rhenium fragment coordinated either to the pyridine ring or, in the case of the benzonitrile ligand, to the tetrazole ring. The electrochemical properties were probed in an imidazolium ionic liquid, highlighting reduction processes centered on the phen ligand and oxidation processes localized on the metal. The photophysical properties of the complexes are characterized by phosphorescent emission from triplet metal-to-ligand charge transfer excited states, with trends in the lifetime and quantum yield in qualitative agreement with the energy gap law. The two dinuclear complexes show almost superimposable emission profiles: in the 5-(4’-cyanophenyl) tetrazolate-bridged complex, the two metal fragments coordinated to the tetrazole are equivalent and share a positive charge of +1. On the other hand, the photophysical properties of the 5-(4’pyridyl)tetrazolate-bridged dinuclear complex suggest energy transfer between the two metal centers

Ligand-induced structural, photophysical, and electrochemical variations in tricarbonyl rhenium(I) tetrazolato complexes

Treatment of [Re(CO)5X] (X = Cl, Br) with 2-(2-tert-butyltetrazol-5-yl)pyridine yielded neutral mononuclear complexes by exchange of two CO ligands for the chelating tetrazolato ligand. Treatment of [Re(CO)5Br] with phenyltetrazolate resulted in the assembly of an anionic dinuclear rhenium tricarbonyl species bridged by three tetrazole rings. The reaction of [Re(CO)5Br] with (2-tert-butyltetrazol-5-yl)benzene formed an analogous neutral dinuclear complex bridged by a tetrazole ring as well as two bromide ligands; however this complex was found to be rather unstable in solution and was only structurally characterized via X-ray diffraction. The first three complexes were investigated for their photophysical properties, highlighting phosphorescent emission from their triplet metal-to-ligand charge transfer excited states, although in the case of the dinuclear species the quantum yield was found to be extremely low. The complexes are also characterized for their electrochemical behavior, and while the neutral mononuclear species show irreversible oxidations, the dinuclear complex displays one reversible and simultaneous two-electron oxidation

Electrochemical Behavior of Chlorine on Platinum Microdisk and Screen-Printed Electrodes in a Room Temperature Ionic Liquid

As a result of the toxic and corrosive nature of chlorine gas, simple methods for its detection are required for monitoring and control purposes. In this paper, the electrochemical behavior of chlorine on platinum working electrodes in the room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][NTf2]) is reported, as a basis for simple sensor devices. Cyclic voltammetry (CV) and chronoamperometry (CA) on a Pt microelectrode revealed the two-electron reduction of Cl2 to chloride ions. On the CV reverse sweep, an oxidation peak due to the oxidation of chloride was observed. The reduction process was diffusion controlled at the concentrations studied (≤4.5% in the gas phase), in contrast to a previous report (J. Phys. Chem. C2008, 112, 19477), which examined only 100% chlorine. The diffusion-controlled currents were linear with gas-phase concentration. Fitting of the CA transients to the Shoup and Szabo expression gave a diffusion coefficient for chlorine in the RTIL of ca. 2.6 × 10–10 m2 s–1. Furthermore, determination of the equilibrium concentration of Cl2 in the RTIL phase as a function of gas-phase concentration enabled a value of 35 to be determined for the Henry’s law dimensionless volatility constant. The electrochemical behavior of chlorine on a Pt screen-printed electrode was also investigated, suggesting that these devices may be useful for chlorine detection in conjunction with suitable RTILs

One-step assembly of Re(I) tricarbonyl 2-pyridyltetrazolato metallacalix[3]arene with aqua emission and reversible three-electron oxidation

The reaction of 2-pyridyltetrazolate with [Re(CO)5X] (X = Cl, Br) yielded the formation of an unexpected cyclic metallacalix[3]-arene, as revealed by X-ray structural studies, characterised by aqua emission and reversible three-electron oxidation

Metal organic frameworks with carbon black for the enhanced electrochemical detection of 2,4,6-trinitrotoluene

The sensing of explosives such as 2,4,6-trinitrotoluene (TNT) directly at an explosion site requires a fast, simple and sensitive detection method, to which electrochemical techniques are well suited. Herein, we report an electrochemical sensor material for TNT based on an ammonium hydroxide (NH4OH) sensitized zinc-1,4–benzenedicarboxylate Zn(BDC) metal organic framework (MOF) mixed with carbon black on a glassy carbon electrode. In the solvent modulation mechanism, by merely changing the concentration of NH4OH during synthesis, two Zn(BDC) MOFs with novel morphologies were fabricated via a hydrothermal approach. The as-prepared MOFs were characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and high-resolution field emission electron microscopy (FESEM) equipped with energy dispersive X-ray spectroscopy (EDS). The different morphologies of the MOFs, and their impact on the performance of the modified electrodes towards the electrochemical detection of TNT was investigated. Under optimum conditions, 0.7–Zn(BDC) demonstrated the best electrochemical response for TNT detection using square wave voltammetry (SWV) with a linear calibration response in the range of 0.3–1.0 M, a limit of detection (LOD) of 0.042 M, a limit of quantification (LOQ) of 0.14 M and a high rate of repeatability. Atomic-scale simulations based on density functional theory authenticated the efficient sensing properties of Zn(BDC) MOF towards TNT. Furthermore, the promising response of the sensors in real sample matrices (tap water and wastewater) was demonstrated, opening new avenues towards the real-time detection of TNT in real environmental samples

Electrochemical Oxidation and Sensing of Methylamine Gas in Room Temperature Ionic Liquids

The electrochemical behaviour of methylamine gas in several room temperature ionic liquids (RTILs), [C2mim][NTf2], [C4mim][NTf2], [C6mim][FAP], [C4mpyrr][NTf2], [C4mim][BF4], and [C4mim][PF6] has been investigated on a Pt microelectrode using cyclic voltammetry. A broad oxidation wave at approximately 3 V, two reduction peaks and another oxidation peak was observed. A complicated mechanism is predicted based on the voltammetry obtained, with ammonia gas as a likely by-product. The currents obtained suggest that methylamine has a high solubility in RTILs, which is important for gas sensing applications. The analytical utility of methylamine was then studied in [C4mpyrr][NTf2] and [C2mim][NTf2]. A linear calibration graph with an R2 value of 0.99 and limits of detection of 33 and 34 ppm were obtained respectively, suggesting that RTILs are favourable non-volatile solvents for the electrochemical detection of highly toxic methylamine gas

Void-Assisted Ion-Paired Proton Transfer at Water-Ionic Liquid Interfaces.

At the water-trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate ([P14,6,6,6 ][FAP]) ionic liquid interface, the unusual electrochemical transfer behavior of protons (H(+) ) and deuterium ions (D(+) ) was identified. Alkali metal cations (such as Li(+) , Na(+) , K(+) ) did not undergo this transfer. H(+) /D(+) transfers were assisted by the hydrophobic counter anion of the ionic liquid, [FAP](-) , resulting in the formation of a mixed capacitive layer from the filling of the latent voids within the anisotropic ionic liquid structure. This phenomenon could impact areas such as proton-coupled electron transfers, fuel cells, and hydrogen storage where ionic liquids are used as aprotic solvents

Recent advances in the use of ionic liquids for electrochemical sensing

Ionic Liquids are salts that are liquid at (or just above) room temperature. They possess several advantageous properties (e.g. high intrinsic conductivity, wide electrochemical windows, low volatility, high thermal stability and good solvating ability), which make them ideal as non-volatile electrolytes in electrochemical sensors. This mini-review article describes the recent uses of ionic liquids in electrochemical sensing applications (covering the last 3 years) in the context of voltammetric sensing at solid/liquid, liquid/liquid interfaces and carbon paste electrodes, as well as their use in gas sensing, ion-selective electrodes, and for detecting biological molecules, explosives and chemical warfare agents. A comment on the future direction and challenges in this field is also presented

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]