223437-11-4Relevant articles and documents
Water-based synthesis of hydrophobic ionic liquids for high-energy electrochemical devices
Montanino, Maria,Alessandrini, Fabrizio,Passerini, Stefano,Appetecchi, Giovanni Battista
, p. 124 - 133 (2013)
In this work is described an innovative synthesis route for hydrophobic ionic liquids (ILs) composed of N-methyl-N-Alkylpyrrolidinium (or piperidinium) or imidazolium or tetralkylammonium cations and (perfluoroalkylsulfonyl)imide, ((CnF2n+
Melting behavior and ionic conductivity in hydrophobic ionic liquids
Kunze, Miriam,Montanino, Maria,Appetecchi, Giovanni B.,Jeong, Sangsik,Schoenhoff, Monika,Winter, Martin,Passerini, Stefano
, p. 1776 - 1782 (2010)
Four room-temperature ionic liquids (RTILs) based on the N-butyl-N-methyl pyrrolidinium (Pyr14 +) and N-methyl-N-propyl pyrrolidinium cations (Pyr13 +) and bis(trifluoromethanesulfonyl)imide (TFSI-) and bis(fluorosulfonyl) imide (FSI-) anions were intensively investigated during their melting. The diffusion coefficients of 1H and 19F were determined using pulsed field gradient (PFG) NMR to study the dynamics of the cations, anions, and ion pairs. The AC conductivities were measured to detect only the motion of the charged particles. The melting points of these ionic liquids were measured by DSC and verified by the temperature-dependent full width at half-maximum (FWHM) of the 1H and 19F NMR peaks. The diffusion and conductivity data at low temperatures gave information about the dynamics at the melting point and allowed specifying the way of melting. In addition, the diffusion coefficients of 1H (DH) and 19F (DF) and conductivity were correlated using the Nernst-Einstein equation with respect to the existence of ion pairs. Our results show that in dependence on the cation different melting behaviors were identified. In the Pyr14based ILs, ion pairs exist, which collapse above the melting point of the sample. This is in contrast to the Pyr 13-based ILs where the present ion pairs in the crystal dissociate during the melting. Furthermore, the anions do not influence the melting behavior of the investigated Pyr14 systems but affect the Pyr 13 ILs. This becomes apparent in species with a higher mobility during the breakup of the crystalline IL.
Esterification in ionic liquids: The influence of solvent basicity
Wells, Thomas P.,Hallett, Jason P.,Williams, Charlotte K.,Welton, Tom
, p. 5585 - 5588 (2008)
(Chemical Equation Presented) The second-order rate constant (k 2) for the esterification of methoxyacetic acid with benzyl alcohol is reported in a range of ionic and molecular solvents. The solvent effects on esterification rate are examined by using a linear solvation energy relationship based on the Kamlet-Taft solvent scales (α, β, and π*). It is shown that the hydrogen bond basicity of the solvent is the dominant parameter in determining the esterification rate and that the best rates are achieved in low basicity solvents.
Effects of acetonitrile on electrodeposition of Ni from a hydrophobic ionic liquid
Zhu, Yan-Li,Katayama, Yasushi,Miura, Takashi
, p. 9019 - 9023 (2010)
The effects of addition of acetonitrile (ACN) on electrodeposition of nickel were investigated in a hydrophobic room-temperature ionic liquid, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (BMPTFSA) containing Ni(TFSA)2. Addition of ACN resulted in the change of the color of the ionic liquid. The UV-vis and FT-IR spectra of the electrolyte showed the coordination environment of Ni(II) changed gradually from [Ni(TFSA)3]- to [Ni(ACN)6]2+ with an increase in the concentration of ACN. The diffusion coefficient of Ni(II) in BMPTFSA was increased and the reduction potential of Ni(II) shifted to the more positive side in the presence of ACN. The nucleation/growth process of Ni was not affected by the change in the coordination environment of Ni(II) from the chronoamperometric results although the more nuclei formed on the electrode surface. SEM showed smoother deposit was obtained in Ni(TFSA) 2/BMPTFSA with ACN.
Cyclic quaternary ammonium ionic liquids with perfluoroalkyltrifluoroborates: Synthesis, characterization, and properties
Zhou, Zhi-Bin,Matsumoto, Hajime,Tatsumi, Kuniaki
, p. 2196 - 2212 (2006)
New cyclic quaternary ammonium salts, composed of N-alkyl(alkyl ether)-N-methylpyrrolidinium, -oxazolidinium, -piperidinium, or -morpholinium cations (alkyl = nC4H9, alkyl ether = CH 3,OCH2, CH3,OCH2CH2) and a perfluoroalkyltrifluoroborate anion ([RFBF3] -, RF = CF3, C2F5, nC3,F7, nC4F9), were synthesized and characterized. Most of these salts are liquids at room temperature. The key properties of these salts - phase transitions, thermal stability, density, viscosity, conductivity, and electrochemical windowswere measured and compared to those of their corresponding [BF4] and [(CF3SO 2)2N]- salts. The structural effect on all the above properties was intensively studied in terms of the identity of the cation and anion, variation of the side chain in the cation (i.e., alkyl versus alkyl ether), and change in the length of the pertluoroalkyl group (RF) in the [RFBF3,]- ion. The reduction of Li + ions and reoxidation of Li metal took place in pure N-butyl-N-methyl pyrrolidinium pentafluoroethyltrifluoroborate as the supporting electrolyte. Such comprehensive studies enhance the knowledge necessary to design and optimize ionic liquids for many applications, including electrolytes. Some of these new salts show desirable properties, including low melting points, high thermal stabilities, low viscosities, high conductivities, and wide electrochemical windows, and may thus be potential candidates for use as electrolytes in high-energy storage devices. In addition, many salts are ionic plastic crystals.
Ag(I)/Ag electrode reaction in amide-type room-temperature ionic liquids
Serizawa, Nobuyuki,Katayama, Yasushi,Miura, Takashi
, p. 346 - 351 (2010)
Ag(I)/Ag electrode reaction was investigated in some amide-type room-temperature ionic liquids composed of different cations. The morphology of silver deposits and the electrochemical behavior were not sensitive to the difference in the cations of ionic liquids. On the other hand, it was suggested that the adsorption of bis(trifluoromethylsulfonyl)amide (TFSA-) is more important for electrodeposition of silver in both ionic liquids and aqueous solutions. The diffusion coefficients of silver cation in the ionic liquids indicated the silver cation is surrounded by TFSA- to form a bulky species. The rate of crystal growth of silver particles in the ionic liquids by electrochemical Ostwald ripening was much slower than that in a nitrate aqueous solution, suggesting the charge transfer in the ionic liquids is slower than that in the aqueous solution.
Solubilizing and Stabilizing Proteins in Anhydrous Ionic Liquids through Formation of Protein-Polymer Surfactant Nanoconstructs
Brogan, Alex P. S.,Hallett, Jason P.
, p. 4494 - 4501 (2016)
Nonaqueous biocatalysis is rapidly becoming a desirable tool for chemical and fuel synthesis in both the laboratory and industry. Similarly, ionic liquids are increasingly popular anhydrous reaction media for a number of industrial processes. Consequently, the use of enzymes in ionic liquids as efficient, environment-friendly, commercial biocatalysts is highly attractive. However, issues surrounding the poor solubility and low stability of enzymes in truly anhydrous media remain a significant challenge. Here, we demonstrate for the first time that engineering the surface of a protein to yield protein-polymer surfactant nanoconstructs allows for dissolution of dry protein into dry ionic liquids. Using myoglobin as a model protein, we show that this method can deliver protein molecules with near native structure into both hydrophilic and hydrophobic anhydrous ionic liquids. Remarkably, using temperature-dependent synchrotron radiation circular dichroism spectroscopy to measure half-denaturation temperatures, our results show that protein stability increases by 55 °C in the ionic liquid as compared to aqueous solution, pushing the solution thermal denaturation beyond the boiling point of water. Therefore, the work presented herein could provide a platform for the realization of biocatalysis at high temperatures or in anhydrous solvent systems.
Physical-Chemical Characterization of Binary Mixtures of 1-Butyl-1-methylpyrrolidinium Bis{(trifluoromethyl)sulfonyl}imide and Aliphatic Nitrile Solvents as Potential Electrolytes for Electrochemical Energy Storage Applications
Neale, Alex R.,Schütter, Christoph,Wilde, Patrick,Goodrich, Peter,Hardacre, Christopher,Passerini, Stefano,Balducci, Andrea,Jacquemin, Johan
, p. 376 - 390 (2017)
In the scope of improving the energy and power densities of electrochemical double layer capacitors (EDLCs), the development of high performance electrolytes with enhanced operative voltages is imperative. The formulation of mixtures containing ionic liquids with organic molecular solvents is an important strategy in the pursuit of developing highly electrochemically stable and safe materials while retaining fast transport properties for high power applications. In this work, we report on the physical-chemical investigations into binary mixtures containing the ionic liquid 1-butyl-1-methylpyrrolidinium bis{(trifluoromethyl)sulfonyl}imide with one mononitrile solvent, butyronitrile, and two dinitrile solvents, glutaronitrile and adiponitrile, as potential electrolytes for EDLCs. The thermal, volumetric, and transport properties of the binary mixtures are investigated as functions of the electrolyte composition and temperature. Furthermore, the electrolyte composition which exhibits the highest conductivity for each of the binary mixtures was determined, and its electrochemical stability is reported using a glassy carbon macrodisk electrode. (Graph Presented).
Electrochemical Preparation of Platinum Nanoparticles from Bis(acetylacetonato)platinum(II) in Some Aprotic Amide-type Ionic Liquids
Sultana, Sharmin,Tachikawa, Naoki,Yoshii, Kazuki,Toshima, Kazunobu,Magagnin, Luca,Katayama, Yasushi
, p. 263 - 270 (2017)
Electrode reaction of bis(acetylacetonato)platinum(II), Pt(acac)2, and preparation of platinum (Pt) nanoparticles have been studied in 1-R-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (R = butyl, hexyl and decyl, which are abbreviated as BMPTFSA, HMPTFSA and DMPTFSA, respectively) ionic liquids by means of cyclic voltammetry and rotating disk electrode (RDE) method. Pt(acac)2 was suggested to be reduced to Pt via a two-electron transfer process at a glassy carbon electrode. The diffusion coefficient of Pt(acac)2 at 50 °C was estimated to be 1.3 × 10?7 cm2 s?1 in BMPTFSA, by RDE measurements. It has been demonstrated that Pt nanoparticles were able to be prepared at the glassy carbon RDE by potentiostatic electrolysis at ?1.8 and ?2.5 V in the ionic liquids containing Pt(acac)2. The prepared nanoparticles were characterized by transmission electron microscopy, energy dispersive X-ray spectroscopy and electron diffraction. No pronounced variation in the average particle sizes of Pt was observed with the rotation rates at the RDE, indicating that the average particle size was independent of the rotation rate or current density. Pt nanoparticles of average sizes of 2.1 ± 0.8, 2.8 ± 0.8 and 3.0 ± 0.8 nm were obtained after electrolysis at ?1.8 V with a rotation rate of 1000 rpm in BMPTFSA, HMPTFSA and DMPTFSA, respectively, suggested that the average particle size may depend on the kind of the ionic liquid.
Does the cation really matter? the effect of modifying an ionic liquid cation on an SN2 process
Tanner, Eden E. L.,Yau, Hon Man,Hawker, Rebecca R.,Croft, Anna K.,Harper, Jason B.
, p. 6170 - 6175 (2013)
The rate of reaction of a Menschutkin process in a range of ionic liquids with different cations was investigated, with temperature-dependent kinetic data giving access to activation parameters for the process in each solvent. These data, along with molecular dynamics simulations, demonstrate the importance of accessibility of the charged centre on the cation and that the key interactions are of a generalised electrostatic nature. The Royal Society of Chemistry.
Newly designed flow reactor as an original method of synthesis of ionic liquids by ion-exchange reactions
Pawlowska-Zygarowicz, Anna
, (2021/11/16)
Optimization of chemical reactions is often costly and requires a significant investment in both materials and time. The solution to this type of difficulty may be the use of continuous flow systems. With the use of the newly designed continuous flow system, the method of synthesizing ionic liquids (ILs) by ion exchange was optimized. The flow rate of the substrates and the selection of the packing of the column in which the reactions were carried out (random packing or a chemical compound in the form of a solid, which was the source of the anion exchanged) were also optimized. The purity of the obtained ionic liquids and the progress of the reaction was determined using ion chromatography. Additionally, for the ionic liquids, which were the starting compounds for the ion exchange reaction, the basic physicochemical properties were determined, thus extending the data library available for chemical compounds belonging to the group of ionic liquids.
Evaluation of ionic liquids as electrolytes for vanadium redox flow batteries
Bahadori, L.,Boyd, R.,Nockemann, P.,Shafeeyan, M. S.,Warrington, A.
, (2020/08/24)
Non-aqueous redox flow batteries (NARFBs) are promising electrochemical energy storage devices due to their wide electrochemical potential windows, generally >2 V of organic solvents. This study aims to investigate the suitability of ionic liquids (ILs) as electrolytes for NARFBs containing a vanadium metal complex. The electrochemistry of a single-component NARFBs employing vanadium (III) acetylacetonate (V(acac)3) was studied in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C4mim][NTF2], and 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, [C4mpyr][NTF2], electrolytes. The electrochemical kinetics of the anodic and cathodic reactions was measured using cyclic voltammetry. The VII/VIII and VIII/VIV couples were quasi-reversible and together yielded a cell potential of 2.2 V in both ILs. Charge/discharge characteristics show that a coulombic efficiency for cycles 1–50 ranged from 88 to 92% using a V(acac)3/[C4mpyr][NTF2] cell.
Binary Mixtures of Aprotic and Protic Ionic Liquids Demonstrate Synergistic Polarity Effect: An Unusual Observation
Thawarkar, Sachin,Khupse, Nageshwar D.,Kumar, Anil
, p. 210 - 221 (2020/02/25)
In this communication, we demonstrate the solute–solvent and solvent–solvent interactions in the binary mixtures of two aprotic ionic liquids, namely 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and 1-butyl-1-methylpyrrolidinium bis(trifl
