Trifluoromethane Sulphonate Research Articles

Physical and Electrical Studies of High Molecular Weight Poly (Methyl Methacrylate) Based Solid Polymer Electrolytes

In this work, the film contained a mixture of PMMA, salt, and plasticizers are studied. PMMA as a host polymer, ammonium trifluoromethane sulphonate or ammonium triflate (NH4CF3SO3) as a doping salt and ethylene carbonate (EC) as a plasticizer is used in this present study. PMMA salt complexes system and plasticized PMMA salt complexes system are prepared by solution cast technique at room temperature. FTIR is used to study the interaction between polymer and salt, and between polymer–salt and plasticizer. The carbonyl group C=O asymmetric stretching mode observed at 1721 cm-1 is broadened and shifted to lower wavenumber when ammonium triflate was added into PMMA. The broadening, shifting and reduction in wavenumbers of FTIR spectra show that the complexation has occurred between the polymer and salt. EIS is performed to measure the electrical conductivity of the polymer–salt system prepared at ambient temperature. The electrical conductivity of film containing 1.0 g of PMMA–35 wt% NH4CF3SO3–16 wt% EC exhibit the highest electrical conductivity with the value of 2.461 x 10-4 S/cm2. XRD is carried out to study the pattern of pure PMMA, PMMA–NH4CF3SO3 and PMMA–NH4CF3SO3–EC. The XRD analysis shows the addition of plasticizer to the polymer–salt system increase the amorphousness of the polymer electrolytes hence increases in conductivity.

Electrochemical deposition of nanocrystalline aluminum from a protic ionic liquid on mild steel

Electrochemically stable new protic ionic liquid (PIL), 1-methylpiperidinium trifluoromethane sulphonate, [HmPip][OTf] was synthesized by mono-step synthetic protocol and synthesized PIL was employed for the electrodeposition of aluminum in ambient conditions. The study reports electrodeposition of aluminum on mild steel in PIL. The cyclic voltammogram of 3.0 M AlCl3 in [HmPip][OTf] is recorded on a mild steel electrode (working electrode) with aluminum as counter as well as reference electrode at 363 K and 0.05 V/s. Potentiostatic electrolysis of AlCl3 in PIL resulted in shiny, bright aluminum deposits which subjected to ex-situ analysis techniques such as FEG-SEM, EDX, and XRD. These findings open up the path for numerous PIL to solve the remaining technological goal in the field of aluminum electrodeposition.

Water-assisted electrochemical fabrication of Cu/Cu2O nanoparticles in protic ionic liquid and their catalytic activity in the synthesis of quinazolinones

The present study reports a simple protocol involving Cu/Cu2O nanoparticles synthesis via electrochemical deposition process in 1-methylpiperidinium trifluoromethane sulphonate [HmPip][OTf] protic ionic liquid. The phase and morphology of the prepared nanoparticles were examined using different characterization techniques such as XRD, XPS, FEG-SEM, TEM, EDX, and FT-IR. A highly efficient, ligand-free method was developed to synthesize quinazolinones from substituted 2-halobenzoic acids with amidines via microwave-assisted Cu/Cu2O nano-catalyst in ethylene glycol as a green solvent. Up to five cycles Cu/Cu2O nanoparticles show good recyclability without loss in its activity.

Electrochemical Fabrication of Copper and Tin Micro‐Crystals from a Protic Ionic Liquid Medium

AbstractNew protic ionic liquid, namely 1‐Methylpiperidinium trifluoromethane sulphonate [HmPip][OTf] was synthesized and employed for the dissolution of Cu and Sn metal precursors followed by the electrodeposition process of the subsequent metals. The cyclic voltammogram of [HmPip][OTf], CuCl2 (80 mM) in [HmPip][OTf] and SnCl2 (65 mM) in [HmPip][OTf] phase recorded at glassy carbon electrode (working electrode), with the glassy carbon as counter and platinum as the reference electrode. The CV indicates that Cu2+ underwent two‐step one‐electron transfer, whereas Sn2+ reduced via one step two‐electron transfer. The diffusion coefficient of Cu1+, Cu2+ and Sn2+ ions in [HmPip][OTf] phase were evaluated by the CV method. The experimental temperature and the scan rate were set at 353 K and 110 mV/s respectively. Electrodeposition of Cu and Sn was done at their corresponding reduction potential determined from cyclic voltammetry. Spectroscopic investigation of the deposits obtained after electrodeposition is done by SEM‐EDX as well as XRD.

Synthesis of Baylis-Hillman adduct under Microwave irradiation using Indium (III) trifluoromethane sulphonate catalyst

Synthesis of Baylis-Hillman adduct under Microwave irradiation using Indium (III) trifluoromethane sulphonate catalyst

Nano lithium aluminate filler incorporating gel lithium triflate polymer composite: Preparation, characterization and application as an electrolyte in lithium ion batteries

Gel polymer composites electrolytes containing nano LiAlO2 as filler were prepared using a solution cast technique and characterized using different techniques such as X-ray diffraction (XRD), thermal analysis (TG, DSC), Fourier transform infra – red spectroscopy (FT-IR) and scanning electron microscope (SEM). X-ray diffraction analysis showed the effect of lithium tri fluoro methane sulphonate (LiCF3SO3), poly vinyl acetate (PVAc) and nano lithium aluminate (LiAlO2) on the crystalline structure of the poly vinylidene fluoride –co– hexa fluoro propylene (PVDF-co-HFP) matrix containing ethylene carbonate (EC) and diethyl carbonate (DEC) as plasticizers. FT-IR analysis confirmed both the good dissolution of the LiCF3SO3 salt and the good interaction of the nano LiAlO2 filler with the polymer matrix. TG analysis showed the good thermal stability of the LiAlO2 samples compared to the free one. Also, addition of nano LiAlO2 filler enhanced the conductivity value of the polymer composites electrolytes. The sample containing 2 wt% of LiAlO2 showed the highest conductivity value, 4.98 × 10−3 Ω −1 cm−1 at room temperature, with good thermal stability behavior (Td = 362 °C). This good conductive and thermally stable polymer nano composite electrolyte was evaluated as a promising membrane for lithium ion batteries application.

Plasticised polymer electrolytes based on PMMA grafted natural rubber–LiCF3SO3–PEG200

Polymer electrolyte membranes that consist of 70 wt-% natural rubber grafted with 30 wt-% poly(methyl methacrylate) (MG30) and 30 wt-% lithium trifluoromethane sulphonate (LiTf) salt have been investigated with various concentrations of poly(ethylene glycol) 200 (PEG200). The formation of polymer–salt complexes has been confirmed by Fourier transform infrared spectral studies. X-ray diffraction studies further confirmed that all the samples prepared are amorphous. The highest conducting sample has the composition of 63 wt-%MG30–27 wt-%LiTf–10 wt-%PEG with conductivity of 3·65×10−4 S cm−1 at 298 K. From differential scanning calorimetry studies, the glass transition temperature Tg is found to increase from −63 to −54°C with the increase in PEG concentration at 30 wt-%PEG200. The ionic transference number of mobile ions has been estimated using Wagner’s polarisation method, and the results reveal that the conducting species are mainly ions.

A Ru II–N-heterocyclic carbene (NHC) complex from metal–metal singly bonded diruthenium(I) precursor: Synthesis, structure and catalytic evaluation

A mononuclear Ru(II)–N-heterocyclic carbene (NHC) complex [Ru II(CO) 2(κ 2C,N-BIN)(H 2O)Br][OTf] (OTf = trifluoromethane sulphonate) ( 1) has been synthesized in high-yield by the oxidative cleavage of the metal–metal singly-bonded diruthenium(I) precursor [Ru 2(CO) 4(CH 3CN) 6(OTf) 2] with 1,8-naphthyridine functionalized NHC precursor 1-benzyl-3-(5,7-dimethyl-1,8-naphthyrid-2-yl)imidazolium bromide (BIN·HBr) at room temperature. Compound 1 catalyzes transfer hydrogenation of ketones to alcohols, and carbene-transfer from ethyl diazoacetate to a variety of substrates. It is shown to be an excellent catalyst for the insertion of carbene into the O–H and N–H bonds of alcohols and amines.

Structural and magnetic characterization of Ni nanoparticles synthesized in ionic liquids

Colloidal suspensions of cubic fcc Ni(0) nanoparticles of 5.0–6.0 nm in sizes were obtained in ionic liquids derived of the 1- n-butyl-3-methylimidazolium cation associated with different anions (tetrafluoroborate (BF 4), trifluoromethane sulphonate (CF 3SO 3), and bis-trifluoromethane-sulfonimidate (N(Tf) 2)). These ionic liquids act as stabilizing agents of the nanoparticles. X-ray diffraction shows clearly Ni(0) nanoparticles embedded in these ionic liquids avoiding their agglomeration. X-ray absorption spectroscopy evidenced that the Ni(0) nanoparticles are surrounded by a cap layer due to the steric and electrostatic interaction with the ionic liquids. Transmission electron microscopy and Small angle X-ray scattering also show a strong evidence of this interaction. The magnetization curves exhibit typical superparamagnetic behavior with no hysteresis. The thermomagnetic curves show superparamagnetic response with blocking temperatures around 200 K.

Synthesis and characterization of catalytic iridium nanoparticles in imidazolium ionic liquids

The reduction of [Ir(cod)Cl] 2 (cod = 1,5-cyclooctadiene) dissolved in 1- n-butyl-3-methyl tetrafluoroborate, hexafluorophosphate and trifluoromethane sulphonate ionic liquids in the presence of 1-decene by molecular hydrogen produces Ir(0) nanoparticles. The formation of these nanoparticles follows the two-step [A → B, A + B → 2B ( k 1 , k 2 )] autocatalytic mechanism. The same mean diameter values of around 2–3 nm were estimated from in situ TEM and SAXS analyses of the Ir(0) nanoparticles dispersed in the ionic liquids and by XRD of the isolated material. XPS and EXAFS analyses clearly show the interactions of the ionic liquid with the metal surface demonstrating the formation of an ionic liquid protective layer surrounding the iridium nanoparticles. SAXS analysis indicated the formation of an ionic liquid layer surrounding the metal particles with an extended molecular length of around 2.8–4.0 nm depending on the type of the anion.

Spectroscopic studies of triflate ion association in polymer gel electrolytes and their constituents

Raman and NMR spectroscopy have been used to investigate the state of ion association in systems comprising salt, polymer and/or solvent. The dissolved salt in each case was lithium triflate (lithium trifluoromethane sulphonate). Five systems were studied, comprising polymer gel electrolytes or constituents of such electrolytes. These were: salted (a) N, N'-dimethyl formamide (DMF), (b) tetraethylene glycol dimethylether (tetraglyme), (c) polyethylene glycol (PEG), (d) end-esterified PEG and (e) poly(vinylidene fluoride) (PVDF) gels containing either DMF or tetraglyme. Raman results give a broad indication of the significance of end-group, solvent and polymer choice in triflate-salted systems. In all cases, anion association rises with temperature, often with a significant increase in ion aggregation. The reliability of these results is supported by an analysis of systematic errors incident in this technique for ion association measurements. A limited comparison performed on the system having the highest concentration of ion aggregates (end-esterified PEG) suggests that Raman and NMR spectroscopy provide different information concerning ion association. Reasons for the difference are discussed, concluding that complementary information is obtained owing to the different time constants relevant to the two techniques and to the dependence of the Raman results on molecular proximity.

Ionic conduction in sequentially ordered thermotropic liquid-crystalline polymers

Main-chain liquid-crystalline polymers containing triad aromatic ester mesogenic blocks together with flexible ion-complexing oligo-oxyethylene blocks have been synthesized. A range of polyoxyethylene precursor polymers was employed with two different triad units to produce mechanically robust polymers exhibiting liquid-crystalline behaviour in the general range 100–200°C. Films were formed consisting of complexes with lithium trifluoromethane sulphonate. Useful ionic conductivities were obtained.

Electrochemical gas sensor using peo electrolyte

A new galvanic sensor for monitoring nitrogen dioxide was developed by using a poly (ethylene oxide) complex of silver trifluoromethane sulphonate electrolyte. The sensor, which is expressed as Au/P(EO) 4.5AgCF 3SO 3/Ag, is a small disk (id, 13 mm). The thickness of gold, film and silver are 25 nm, 30 μm and 1 mm, respectively. The current flowing in the external circuit of the cell was linearly related to the concentration of nitrogen dioxide from 20 ppb to about 10 ppm.

Polyethylene oxide with lithium trifluoromethane sulphonate; an NMR study

A study of the NMR parameters of a range of high-molecular-weight poly(ethylene oxide) samples doped with substantial concentrations of lithium trifluoromethane sulphonate is reported. The measurements, taken over a range of temperatures from 100 to 370 K, include (i) the T1 values of fluorine, protons, and lithium, (ii) the ratios of the amplitudes of the different types of signals from one nuclear species, measured for each of the nuclear species present, and (iii) the ratios of the amplitudes of the signals from the fluorine and lithium nuclei. The main impact of the study is to present evidence against the simple partition of the NMR signals into crystalline and elastomeric portions and to document the observation that significant numbers of lithium nuclei are not observed by the NMR technique, strongly suggesting that there are inequivalent lithium sites.

ChemInform Abstract: The Application of the Trichloroacetimidate Method to the Synthesis of α‐D‐Gluco‐ and α‐D‐Galactopyranosides.

Abstract The trichloroacetimidate method has been applied to the construction of α-d-galacto- and α-d-glucopyranosides. The readily available β-trichloroacetimidates of 2,3,4,6-tetra-O-benzyl-d-galacto- and glucopyranose (1-β and 3-β, respectively) have been employed in glycosidations with several monosaccharides (either A, B, C or D) under varying experimental conditions. With the galactose derivative 1-β as a donor and each of the monosaccharides A-D as acceptors, the corresponding disaccharides 1A-1D, were obtained in high yield and with good α-stereoselectivity when employing diethyl ether as solvent and either trimethylsilyl- or tert-butyldimethylsilyl trifluoro-methane sulphonate as catalyst. Glycosidations with the glucose derivative 3-β, as donor, and with the monosaccharide acceptors A, B or D, gave the corresponding disaccharides 3A, 3B and 3D, in high yield but with somewhat lower α-diastereoselectivity than observed with the galactose derivative 1-β. The stereochemical outcome of the reactions...

The Application of the Trichloroacetimidate Method to the Synthesis of α-D-Gluco- and α-D-Galactopyranosides

Abstract The trichloroacetimidate method has been applied to the construction of α-d-galacto- and α-d-glucopyranosides. The readily available β-trichloroacetimidates of 2,3,4,6-tetra-O-benzyl-d-galacto- and glucopyranose (1-β and 3-β, respectively) have been employed in glycosidations with several monosaccharides (either A, B, C or D) under varying experimental conditions. With the galactose derivative 1-β as a donor and each of the monosaccharides A-D as acceptors, the corresponding disaccharides 1A-1D, were obtained in high yield and with good α-stereoselectivity when employing diethyl ether as solvent and either trimethylsilyl- or tert-butyldimethylsilyl trifluoro-methane sulphonate as catalyst. Glycosidations with the glucose derivative 3-β, as donor, and with the monosaccharide acceptors A, B or D, gave the corresponding disaccharides 3A, 3B and 3D, in high yield but with somewhat lower α-diastereoselectivity than observed with the galactose derivative 1-β. The stereochemical outcome of the reactions...

Composite electrodes

A model is developed to describe the performance of composite electrodes - i.e. polycrystalline insertion electrodes bound with a solid electrolyte - in solid state batteries. By solving the Nernst-Planck equation in terms of the ionic conductivities of the electrode and electrolyte together with the Faradaic capacity of the electrode, the composite is represented by a network of electrical components. A.c. and d.c. experiments are presented to illustrate the influence of grain size, relative conductivities and other parameters of the materials with particular reference to the electrodes V6O13, LiAl and the electrolyte polyethylene oxide lithium trifluoromethane sulphonate.

The structure of the addition compound of tris-(N,N-dimethylacetamide) hexaaquo praseodymium trifluoromethane sulphonate

The structure of the addition compound of tris-(<i>N</i>,<i>N</i>-dimethylacetamide) hexaaquo praseodymium trifluoromethane sulphonate

Organomercury Compounds : XXIV Facile syntheses of polyfluoroarylmercurials by mercuration reactions

The polyfluoroarylmercuric chlorides, RHgCl (R = C 6F 5, p -MeOC 6F 4, p -MeC 6F 4, m -HC 6F 4, o -HC 6F 4, p -HC 6F 4, m -O 2NC 6F 4, o -O 2NC 6F 4, p -BrC 6F 4, m -BrC 6F 4, o -BrC 6F 4, p -HOC 6F 4, p -H 2NC 6F 4, m -HO 2CC 6F 4, p -( p -HC 6F 4)C 6F 4, 3,5-H 2C 6F 3, 3-bromo-2,4,6-trifluorophenyl or 3-bromo-2,5,6-trifluorophenyl), and the bis (polyfluorophenyl)mercurials, R 2Hg (R = C 6F 5, p -MeOC 6F 4, p -MeC 6F 4, p -HC 6F 4, m -O 2NC 6F 4, o -O 2NC 6F 4, p -BrC 6F 4, m -BrC 6F 4, o -BrC 6F 4, p -HOC 6F 4, or p -H 2NC 6F 4) have been prepared by mercuration of the appropriate polyfluoroarenes with mercuric trifluoroacetate and trifluoromethanesulphonic acid in trifluoroacetic acid, followed by treatment of the products with hydrochloric acid (RHgCl derivatives) or potassium bromide (R 2Hg derivatives). For R = p -MeOC 6F 4, the actual mercuration product has been isolated and identified as 2,3,5,6-tetrafluoro-4-methoxyphenylmercuric trifluoromethane sulphonate. Interaction of mercuric trifluoroacetate with trifluoromethanesulphonic acid in trifluoroacetic acid yields mercuric trifluoromethanesulphonate, which is considered to be the mercurating agent, and which has been characterized as the complex, [Hg(bpy) 3](O 3SCF 3) 2·H 20 (bpy = 2,2′-bipyridyl). The mercuration syntheses are very simple and convenient, and should become the preferred method for most polyfluoroarylmercurials.

Photocatalysis (II) photochemical cycloadditions of cyclohexenes and cycloheptene with conjugated dienes catalysed by copper (I) trifluoromethane sulphonate

Photocatalysis (II) photochemical cycloadditions of cyclohexenes and cycloheptene with conjugated dienes catalysed by copper (I) trifluoromethane sulphonate