A Detailed Study of the (Electro)chemical Behavior of Bis(trifluoromethanesulfonyl)imide Based Ionic Liquids at Different Purification Steps

Merli, Daniele; Protti, Stefano; Petracca, Paola; Fagnoni, Maurizio; Profumo, Antonella

doi:10.1002/elan.201300013

Cited by 4 publications

(7 citation statements)

References 53 publications

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“…Creating a broadly applicable theoretical model for the IL EDL accounting for the various physical properties and testing the models experimentally has proven challenging. Specifically, literature reports of IL electrochemical properties show significant variation for protic versus aprotic ILs and for specific electrode surfaces (metallic, nonmetallic, and semiconductor). , Variability in purity (water and halides are common contaminants), however, is also a major issue in many IL studies.…”

Section: Introductionmentioning

confidence: 99%

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Large-Amplitude Fourier-Transformed AC Voltammetric Study of the Capacitive Electrochemical Behavior of the 1-Butyl-3-methylimidazolium Tetrafluoroborate–Polycrystalline Gold Electrode Interface

2017

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In this paper, the capacitive electrochemical behavior of the 1-butyl-3methylimidazolium tetrafluoroborate (Bmim BF 4 )−polycrystalline gold electrode interface is reported over the potential range from −0.37 to 0.53 V vs Fc/Fc + (Fc = ferrocene). Experimental results are generated by analysis of data (RC model) obtained from largeamplitude Fourier-transformed alternating current voltammetry (FT-ACV) over the frequency range of 10 Hz to 1 kHz. Results suggest a parabolic, U-shaped capacitance versus potential relationship, in stark contrast to present ionic liquid (IL) electrochemical double-layer (EDL) theory. The potential range analyzed was carefully selected to be free of Faradaic current and displays minimal hysteresis with respect to the potential scan direction. Over the selected potential window spanning 0.9 V, the capacitance versus potential curve at 9 Hz exhibits a Ushape, with a capacitance minimum of 19.9 ± 1.3 μF cm −2 at 0.13 ± 0.04 V, flanked by maximum values of 21.2 ± 1.3 and 20.8 ± 1.4 μF cm −2 at −0.37 and 0.53 V vs Fc/Fc + , respectively. This capacitance versus potential profile is consistent with traditional Gouy−Chapman−Stern theory for dilute aqueous electrolyte solutions and high-temperature molten salts but distinctly misaligned with bell-or camel-shaped relationships that have recently been proposed in IL model systems. The minimum capacitance exhibits a small level of frequency dispersion, which increases linearly versus the logarithm of the applied frequency. The potential at which the minimum capacitance is located is also slightly dependent on frequency. This work demonstrates that large-amplitude FT-ACV provides a sensitive probe of the EDL from a single experiment and advances the convergence between theoretical predictions and experimental observations of IL−electrode EDL systems.

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Section: Introductionmentioning

confidence: 99%

“…Specifically, literature reports of IL electrochemical properties show significant variation for protic versus aprotic ILs and for specific electrode surfaces (metallic, nonmetallic, and semiconductor). 7,8 Variability in purity (water and halides are common contaminants), however, is also a major issue in many IL studies.…”

Section: ■ Introductionmentioning

confidence: 99%

Large-Amplitude Fourier-Transformed AC Voltammetric Study of the Capacitive Electrochemical Behavior of the 1-Butyl-3-methylimidazolium Tetrafluoroborate–Polycrystalline Gold Electrode Interface

2017

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“…One area not yet fully explored is in the area of recycling cellulose and other organic materials or biomass pretreatment. 10 Thermogravimetric combined with mass spectrometric analysis is one possibility to detect fragments and traces to understand decomposition mechanisms and detect impurities and decomposition products. 5 Another eld of interest is engineering applications with special technical requirements for ILs such as electrolytes for alkali-metal electrochemical devices, lubricants or polymers for solar cells as well as water splitting fuel cells.…”

Section: Introductionmentioning

confidence: 99%

Stability studies of ionic liquid [EMIm][NTf₂] under short-term thermal exposure

et al. 2016

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Ionic liquids (ILs) as new media for synthesis and as functional fluids in technical applications are still of high interest. Cooling a steel component from an annealing temperature of nearly 850 C down to room temperature in a liquid bath is a technically important process. The use of ionic liquids offers advantages avoiding film boiling of the quenching medium. However, such a high immersion temperature exceeds the thermal stability of the IL, for example such as [EMIm][NTf 2 ]. To obtain information about formation of potential toxic decomposition products, potential fragments at varied states of decomposition of [EMIm][NTf 2 ] were studied by various spectroscopic and gravimetric methods. For the first time it was possible to quantify fluorine-containing products via mass spectrometry coupled directly with thermogravimetric (TG) measurements. While chemical and spectroscopic analysis of thermally stressed ILs revealed no hints concerning changes of composition after quenching hot steel for several times, the mass-spectrometer (MS) coupled TG analysis gives information by comparing the decomposition behaviour of fresh and used ILs. A number of fragments were detected in low amounts confirming the proposed decomposition mechanism.Fig. 1 Chemical structure of [EMIm][NTf 2 ].

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“…All ILs were prepared from the corresponding halides (chloride, bromide, or iodide) and purified following published procedures . Briefly, the halide salts were obtained in almost quantitative yields by reacting N -methyl pyrrolidine with butyl iodide (IL 1 ), 2-bromoethyl methyl ether (ILs 2 and 4 ), or 2-methoxyethoxymethyl chloride (IL 3 ) in ethyl acetate.…”

Section: Methodsmentioning

confidence: 99%

Pyrrolidinium-based Ionic Liquids: Aquatic Ecotoxicity, Biodegradability, and Algal Subinhibitory Stimulation

Samorì

Campisi

Fagnoni

et al. 2015

ACS Sustainable Chem. Eng.

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Pyrrolidinium imides are considered among the most promising electrolytes for the development of novel and sustainable portable energy devices. Because of this widespread potentiality, a risk scenario of an erroneous disposal of ionic liquids-based batteries in the environment has to be taken into account. In the present study some of the best energy performing pyrrolidinium-based ionic liquids were evaluated in terms of persistence in aquatic environments and hazard towards freshwater organisms (the crustacean Daphnia magna and the unicellular green alga Raphidocelis subcapitata). The examined ionic liquids were not aerobically biodegradable (biodegradation less than 5% in 28 days) but they demonstrated low toxicity towards algae and crustaceans, according to the standard bioassay endpoints (EC 50 > 100 mg L -1 ). However, ionic liquids were able to alter the cellular morphology of R. subcapitata and an increased amount of proteins (30%) was observed in the exposed cells, suggesting an inhibition of cellular division. rpm for 10 min, washed with a physiological saline solution and then centrifuged again; this procedure was repeated 3 times in order to assure the removal of any eventual IL trace on algal surfaces. Then algal cells were freeze-dried and analyzed to determine their nitrogen (by elemental analysis), protein (by the Lowry protocol 27 ) and lipid (by GC-MS) content. Ammonium (NH 3 -N, mg L -1 ) was measured at day 0 and after 72 h in the filtrate through test kit colorimetric analyses (DR/2010; Hach, Colorado, USA), by using the Nessler Method. 33Algae were also exposed to a concentration of 0.9 mM of 2 under the dark and using 2 as the sole N-source in the growth medium (OECD medium prepared with all nutrients besides NH 4 Cl).Controls were run in parallel in each experiment.The biovolume determination was performed in accordance to the literature 25 : 20 cells were randomly selected and the sizes (length and width) were measured. Elemental analyses were performed by using an elemental analyzer (Thermo Scientific, Flash 2000, Organic Elemental Analyzer) by means of the flash combustion technique. The fatty acid methyl esters (FAMEs) content of algal cells (indicator of the lipid amount) was determined as follows: samples (about 2 mg) were suspended in dimethyl carbonate (0.4 mL).2,2-Dimethoxypropane (0.1 mL) and 0.5 M NaOH in MeOH (0.1 mL) were then added; the samples were placed in an incubator at 90°C for 30 min. After cooling for 5 min to room temperature, 1.3 M BF 3 -methanol 10% (w/w) reagent (0.7 mL) was added before repeating the incubation for 30 min. After cooling for 5 min to room temperature, saturated NaCl aqueous solution (2 mL) and hexane (1 mL) containing methyl nonadecanoate (internal standard for GC-MS quantification, 0.02 mg) were added and the samples were centrifuged at 4000 rpm for 1 min. The upper hexane-dimethylcarbonate layer, containing FAMEs, was transferred to vials for GC-MS analysis. Each analysis was repeated in duplicate. The relative response factors used for the quant...

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A Detailed Study of the (Electro)chemical Behavior of Bis(trifluoromethanesulfonyl)imide Based Ionic Liquids at Different Purification Steps

Cited by 4 publications

References 53 publications

Large-Amplitude Fourier-Transformed AC Voltammetric Study of the Capacitive Electrochemical Behavior of the 1-Butyl-3-methylimidazolium Tetrafluoroborate–Polycrystalline Gold Electrode Interface

Large-Amplitude Fourier-Transformed AC Voltammetric Study of the Capacitive Electrochemical Behavior of the 1-Butyl-3-methylimidazolium Tetrafluoroborate–Polycrystalline Gold Electrode Interface

Stability studies of ionic liquid [EMIm][NTf₂] under short-term thermal exposure

Pyrrolidinium-based Ionic Liquids: Aquatic Ecotoxicity, Biodegradability, and Algal Subinhibitory Stimulation

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A Detailed Study of the (Electro)chemical Behavior of Bis(trifluoromethanesulfonyl)imide Based Ionic Liquids at Different Purification Steps

Cited by 4 publications

References 53 publications

Large-Amplitude Fourier-Transformed AC Voltammetric Study of the Capacitive Electrochemical Behavior of the 1-Butyl-3-methylimidazolium Tetrafluoroborate–Polycrystalline Gold Electrode Interface

Large-Amplitude Fourier-Transformed AC Voltammetric Study of the Capacitive Electrochemical Behavior of the 1-Butyl-3-methylimidazolium Tetrafluoroborate–Polycrystalline Gold Electrode Interface

Stability studies of ionic liquid [EMIm][NTf2] under short-term thermal exposure

Pyrrolidinium-based Ionic Liquids: Aquatic Ecotoxicity, Biodegradability, and Algal Subinhibitory Stimulation

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Stability studies of ionic liquid [EMIm][NTf₂] under short-term thermal exposure