The Kinetics of Ferrocene Volatilisation from an Ionic Liquid

Fu, Chaopeng; Aldous, Leigh; Dickinson, Edmund J. F.; Manan, Ninie Suhana Abdul; Compton, Richard G.

doi:10.1002/cphc.201100204

Cited by 18 publications

(23 citation statements)

References 28 publications

(65 reference statements)

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“…The first ionic liquid redox system under investigation is the oxidation of ferrocene (Equation 3). This process has been reported previously 28 [29] and is employed here as a highly reversible one‐electron redox reaction…”

Section: Resultsmentioning

confidence: 97%

Electrochemical Properties of Spinel Cobalt Ferrite Nanoparticles with Sodium Alginate as Interactive Binder

et al. 2014

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We introduce a process of making high‐capacity and rate‐capable metal‐ferrite‐based conversion anodes for lithium‐ion batteries. Cobalt ferrite (CoFe2O4) exhibits a discharge capacity that is two‐times higher compared to the state‐of‐the‐art graphite anode, but at the same time it shows high volume change (ca. 95 %) during conversion reaction with lithium in an electrochemical environment. This large volume expansion is responsible for the particle–particle and conductive‐carbon particles–active materials detachment, which leads to cyclic instability during subsequent cycles. As observed in our earlier work, any kind of weak or strong chemical interaction between active materials and binder is necessary to achieve excellent electrochemical performance in case of conversion or alloying reactions. To compare the electrochemical activity of CoFe2O4 nanoparticles against lithium, we use conventional polyvinylidene fluoride and sodium alginate binder to fabricate electrodes. Fourier‐transform infrared measurements reveal weak hydrogen‐bond formation between surface OH groups of CoFe2O4 and COOH groups of the alginate binder. Indentation tests further confirm the increased hardness of the alginate/CoFe2O4‐based electrode films. CoFe2O4–alginate–carbon anode exhibits a high specific capacity of 890 mAh g−1 at 0.1 C rate (91.4 mA g−1) after 50 charge–discharge cycles. Even at high rate cycling with current densities such as 18280 mA g−1 (20 C), the same electrode material exhibits a specific capacity of 470 mAh g−1, which is much higher than that of conventional graphite anode at the same electrochemical conditions.

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Section: Resultsmentioning

confidence: 97%

Electrochemical Properties of Spinel Cobalt Ferrite Nanoparticles with Sodium Alginate as Interactive Binder

et al. 2014

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“…The cyclic voltammetry was conducted on a 11.0 µm diameter platinum microelectrode in a [C 4 mpyrr][NTf 2 ] solution containing ZrCl 4 under vacuum, housed in a specially designed glass ‘T‐cell’ (for full experimental details please see 15). Cyclic voltammetry in the predried [C 4 mpyrr][NTf 2 ] was conducted in a three‐electrode set‐up consisting of Pt microdisk as the working electrode, Pt wire as the counter electrode and a Ag wire as the reference electrode.…”

Section: Methodsmentioning

confidence: 99%

Electrochemistry of Zirconium Tetrachloride in the Ionic Liquid N‐Butyl‐N‐methylpyrrolidinium Bis(trifluoromethylsulfonyl)imide: Formation of Zr(III) and Exploitation of ZrCl₄ as a Facile Ionic Liquid Drying Agent

Aldous

Manan

et al. 2011

Electroanalysis

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The electrochemistry of zirconium tetrachloride in the ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide has been studied, and the one electron reduction is proved by chronoamperometry. Furthermore, we report the application of ZrCl 4 as a facile and general ionic liquid drying agent for use in voltammetry. [3]. Ionic liquids (ILs) are important media for the electrochemical research of species which cannot be studied in aqueous solution. ILs not only have much wider electrochemical windows than regular solvents, often wider than 6 V [2] and thus allowing for electrodeposition of various semiconductors and metals [4], but they also can stabilise some compounds that would normally undergo hydrolysis in aqueous solutions, allowing for studies on water-sensitive species such as PCl 3 [5].In this work, we report the electrochemistry of zirconium tetrachloride (ZrCl 4 ) in the ionic liquid N-butyl-Nmethylpyrrolidinium bis(trifluoromethylsulfonyl)imide [C 4 mpyrr][NTf 2 ]. ZrCl 4 is the main source for production of Zr metal and Zr-based alloys [6], which are important materials and have been widely used in applications such as corrosion-resistant materials, as well as catalysts for various processes [7]. Little data on the electrochemistry of ZrCl 4 in ionic liquids has been hitherto reported. This paucity of information likely arises from its volatility and rapid hydrolysis. ZrCl 4 is readily volatile and very sensitive to air, which makes it difficult to study electrochemically in any detail. To the best of our knowledge, only Tsuda et al. have reported the electrochemistry of Zr(IV) in aluminium chloride-1-ethyl-3-methylimidazolium chloride (66.7-33.3 mol %, respectively) at 353 K [8]. However, since more and more air and moisture stable ILs have been synthesized, there is much interest in non-haloaluminate room temperature ionic liquids. The present study reports not only the electrochemistry of ZrCl 4 but also its application as a facile ionic liquid drying agent. Figure 1 shows the voltammetry of ZrCl 4 in [C 4 mpyrr]-[NTf 2 ], after being dried under vacuum prior to measurement. A limiting reduction current with a half-wave potential of 0.08 V and an oxidation peak current with a peak potential of 0.70 V are clearly visible. Interestingly, the oxidation peak remains the same size as a function of time under vacuum, while the charge under the peak remained constant over a range of scan rates and had a charge characteristic with a monolayer (see below). In contrast the reduction wave steadily decreased over time, since the ZrCl 4 concentrations could not be stabilised in the ionic liquid even if it was put under vacuum for drying for 24 h beforehand, as it both undergoes rapid hydrolysis and is extremely volatile. Thus additions of various concentrations of ZrCl 4 resulted in reductive voltammetry that did not scale with concentration and a white precipitate was always present regardless the concentra-210

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“…The peak current response of ferrocene was low as ferrocene is volatile in most of the ionic liquids studied which leads to a reduction in concentration when treated under vacuum conditions. [18][19][20] The peak potential is obtained using square wave voltammetry as this technique records the current in both reductive and oxidative directions at each potential step and hence the peak potential in square wave voltammetry is the mid way potential and very close to the formal potential of the redox couple studied. 21,22 Fig.…”

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confidence: 99%

Tuning solute redox potentials by varying the anion component of room temperature ionic liquids

et al. 2012

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The electrode potentials for the two one electron oxidations of 1,2-diferrocenylethylene (bisferrocene, BF) were studied relative to that of the one electrode oxidation of decamethylferrocene in a variety of RTILs. The difference in these potentials was found to be very sensitive to the anion component of the ionic liquid showing the scope of these solutes as 'designer media' to tune the thermodynamic properties of solutes dissolved in them.

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The Kinetics of Ferrocene Volatilisation from an Ionic Liquid

Cited by 18 publications

References 28 publications

Electrochemical Properties of Spinel Cobalt Ferrite Nanoparticles with Sodium Alginate as Interactive Binder

Electrochemical Properties of Spinel Cobalt Ferrite Nanoparticles with Sodium Alginate as Interactive Binder

Electrochemistry of Zirconium Tetrachloride in the Ionic Liquid N‐Butyl‐N‐methylpyrrolidinium Bis(trifluoromethylsulfonyl)imide: Formation of Zr(III) and Exploitation of ZrCl₄ as a Facile Ionic Liquid Drying Agent

Tuning solute redox potentials by varying the anion component of room temperature ionic liquids

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The Kinetics of Ferrocene Volatilisation from an Ionic Liquid

Cited by 18 publications

References 28 publications

Electrochemical Properties of Spinel Cobalt Ferrite Nanoparticles with Sodium Alginate as Interactive Binder

Electrochemical Properties of Spinel Cobalt Ferrite Nanoparticles with Sodium Alginate as Interactive Binder

Electrochemistry of Zirconium Tetrachloride in the Ionic Liquid N‐Butyl‐N‐methylpyrrolidinium Bis(trifluoromethylsulfonyl)imide: Formation of Zr(III) and Exploitation of ZrCl4 as a Facile Ionic Liquid Drying Agent

Tuning solute redox potentials by varying the anion component of room temperature ionic liquids

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Electrochemistry of Zirconium Tetrachloride in the Ionic Liquid N‐Butyl‐N‐methylpyrrolidinium Bis(trifluoromethylsulfonyl)imide: Formation of Zr(III) and Exploitation of ZrCl₄ as a Facile Ionic Liquid Drying Agent