The structure of bis(trifluoromethanesulfonyl) imide (TFSI-) in the liquid state has been studied by means Raman spectroscopy and DFT calculations. spectra 1-ethyl-3-methylimidazolium (EMI+) TFSI- show relatively strong bands arising from at about 398 407 cm(-1). Interestingly, cm(-1) band, relative to one, is appreciably intensified with raising temperature, suggesting that an equilibrium established between conformers state. According calculations followed normal frequency analyses, two C2...

The solvation structure of the lithium ion in room-temperature ionic liquids 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide (EMI(+)TFSI(-)) and N-butyl-N-methylpyrrolidinium (BMP(+0TFSI(-)) has been studied by Raman spectroscopy DFT calculations. spectra EMI(+)TFSI(-) BMP(+)TFSI(-) containing Li(+)TFSI(-) over range 0.144-0.589 0.076-0.633 mol dm(-3), respectively, were measured at 298 K. A strong 744 cm-1 band free TFSI(-) bulk weakens with increasing concentration ion, it...

Highly stretchable and self-healing polymer gels formed solely by physical entanglements of ultrahigh-molecular weight (UHMW) polymers were fabricated through a facile one-step process. Radical polymerization vinyl monomers in ionic liquids under very low initiator concentration conditions produced UHMW more than 106 g/mol with nearly 100% yield, resulting the formation physically entangled transparent gels. The showed excellent properties, such as high stretchability, conductivity,...

Raman spectra of liquid 1-ethyl-3-methylimidazolium (EMI+) salts, EMI+BF4-, EMI+PF6-, EMI+CF3SO3-, and EMI+N(CF3SO2)2-, were measured over the frequency range 200−1600 cm-1. In 200−500 cm-1, we found five bands originating from EMI+ ion at 241, 297, 387, 430, 448 However, cm-1 band could hardly be reproduced by theoretical calculations in terms a given conformer, implying that originates another conformer. This is expected because involves an ethyl group bound to N atom imidazolium ring, can...

The liquid structure of 1-ethyl-3-methylimidazolium bis-(trifluoromethanesulfonyl) imide (EMI(+)TFSI(-)) has been studied by means large-angle X-ray scattering (LAXS), (1)H, (13)C, and (19)F NMR, molecular dynamics (MD) simulations. LAXS measurements show that the ionic is highly structured with intermolecular interactions at around 6, 9, 15 A. A are ascribed, on basis MD simulation, to nearest neighbor EMI(+)...TFSI(-) interaction, EMI(+)...EMI(+) TFSI(-)...TFSI(-) interactions, second...

Short- and long-range liquid structures of [C(n)mIm(+)][TFSA(-)] with n = 2, 4, 6, 8, 10, 12 have been studied by high-energy x-ray diffraction (HEXRD) small-angle neutron scattering (SANS) experiments the aid MD simulations. Observed structure factor, S(Q), for ionic liquids alkyl-chain length > 6 exhibited a characteristic peak in low-Q range 0.2-0.4 Å(-1), indicating heterogeneity their liquids. SANS profiles I(H)(Q) I(D)(Q) normal alkyl group deuterated liquids, respectively, showed...

Raman spectra of 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)amide [C2mIm+][FSA–] ionic liquid solutions dissolving LiFSA salt various concentrations were measured at 298 K. FSA– ((FSO2)2N–) is an analogue anion bis(trifluoromethanesulfonyl)amide ((CF3SO2)2N–; TFSA–). We found that a solvation number the Li+ ion in 3, though it has been well established solvated by two TFSA– anions corresponding liquids below mole fraction xLi+ < 0.2. To yield further insight into larger numbers, higher...

Room-temperature ionic liquids (RTIL, IL) are stable composed of anions and cations. N-methyl-N-propyl-pyrrolidinium (P13, Py13, PYR13, or mppy) is an important cation produces ILs with various anions. In this study two amide-type anions, bis(trifluoromethanesulfonyl)amide [N(SO2CF3)2, TFSA, TFSI, NTf2, Tf2N] bis(fluorosulfonyl)amide [N(SO2F)2, FSA, FSI], were investigated. addition to P13-TFSA P13-FSA, lithium salt doped samples prepared (P13-TFSA-Li P13-FSA-Li). The individual ion...

In this paper, we show a free-standing highly ion-conducting ionic liquid (IL)-polymer electrolyte, Tetra-PEG ion gel, prepared by incorporating imidazolium-based ILs into very much lower concentration (3–6 wt%) of tetra-arm poly(ethylene glycol), Tetra-PEG. The conductivities the gels were nearly equal to those pure ILs, indicating realization liquid-like conductivity in solid-state material. showed advanced mechanical properties demonstrated results compression and stretching tests.

We evaluate the homogeneity of Tetra-PEG gel and examine models predicting rubber elasticity. Infrared spectroscopy revealed near absence dangling chains. Concentration dependence number elastically effective chains ineffective loops validity phantom network model. These data suggest that is close to an ideal polymer model true describing contribution chemical cross-link elasticity a swollen network.

Liquid structure and the closest ion–ion interactions in a series of primary alkylammonium nitrate ionic liquids [CnAm+][NO3–] (n = 2, 3, 4) were studied by means high-energy X-ray diffraction (HEXRD) experiments with aid molecular dynamics (MD) simulations. Experimental density factors are good accordance those evaluated MD With regard to liquid structure, characteristic peaks appeared low Q (Q: scattering vector) region S(Q)'s for all here, they increased intensity peak position shift...

The conformational landscapes of two commonly used ionic liquid ions, the anion bis(trifluoromethanesulfonyl)amide (Ntf2) and cations N-propyl- N-butyl-N-methylpyrrolidinium, were investigated using data obtained from Raman spectroscopy, molecular dynamics, ab initio techniques. In case Ntf2, plotting three-dimensional potential energy surfaces (PES) corresponding dynamics (MD) simulations confirmed existence stable isomers (each existing as a pair enantiomers) evidenced nature flexible,...

Raman spectra of the ionic liquid, 1-butyl-3-methylimidazolium bis-(trifluoromethanesulfonyl)amide [C(4)mIm][TFSA] containing a LiTFSA salt were measured for lithium mole fractions x(Li) = 0.000, 0.053, 0.106, and 0.171 in temperature range 273-350 K. The ion solvation number 2 at ambient is kept constant higher temperatures examined this study. Thermodynamic quantities, such as Gibbs free energy, Delta(iso)G(0); enthalpy, Delta(iso)H(0); entropy, Delta(iso)S(0), conformational isomerism...

Liquid structures of the bis(trifluoromethanesulfonyl)amide based ionic liquids composed 1-ethyl-3-methylimidazolium and N-methyl-N-propylpyrrolidinium ([C(2)mIm(+)][TFSA(-)] [C(3)mPyrro(+)][TFSA(-)], respectively) Li(+) ion solvation structure in their lithium salt solutions were studied by means high-energy X-ray diffraction (HEXRD) technique with aid MD simulations. With regard to neat liquids, a small but significant difference was found at around 3.5 Å intermolecular radial distribution...

We carried out a kinetic study on the gelation reaction of AB-type cross-end coupling two tetra-arm poly(ethylene glycol) (Tetra-PEG) prepolymers having amine (Tetra-PEG-NH2) and activated ester (Tetra-PEG-NHS) terminal groups by ATR-IR UV spectroscopies. The rate constant for Tetra-PEG, kgel, was determined in aqueous solutions with varying both prepolymer volume fraction, ϕ, molecular weight, Mw, prepolymers. It clearly found that value kgel is independent ϕ comparable to corresponding...

We report here structural study on solvation of Mg2+ ion in triglyme (G3)-based solutions applying as a novel electrolyte for rechargeable Mg batteries. In Mg(TFSA)2/G3 (TFSA = bis(trifluoromethanesulfonyl)amide), we found from Raman spectroscopy that is solvated with two G3 molecules to form [Mg(G3)2]2+ complexes. No direct coordination TFSA– anion occurs the salt concentrations cMg 0–1.60 M. The geometries and interaction energies were evaluated by DFT calculations indicated most stable...

We report the relation between structural and electrochemical properties of N,N-dimethylformamide (DMF)-based electrolytes containing lithium bis(trifluoromethanesulfonyl)amide (LiTFSA) in concentration range cLi = 0–3.2 mol dm–3. Raman spectroscopy DFT calculations indicate that Li+ ions are solvated by DMF molecules form [Li(DMF)4]+ complexes at low (<2.0 dm–3, LiTFSA:DMF 1:4 mol), whereas coordination TFSA– anions to occurs gradually increases as above 2.0 Quantitative data analysis...

A fluorine-doped tin oxide-coated glass electrode modified with a bilayer film of underlying α-Co(OH)2 and overlying Mg-intercalated Co-doped δ-type (layered) MnO2 (Mg|Co-MnO2) preferentially yielded oxygen Faradaic efficiency as high 79% in the presence chloride ions at concentration (0.5 M). This noble metal-free was fabricated by cathodic electrolysis aqueous Co(NO3)2 followed anodic mixture Mn2+, Co2+, cetyltrimethylammonium (CTA+) water. The CTA+ accommodated interlayer spaces δ-MnO2...

We fabricated a thin film of layered MnO2 whose interlayer space was occupied by hydrated Ni2+ and Cu2+ ions. The process consisted electrodeposition intercalated with tetrabutylammonium cations (TBA+) anodic oxidation aqueous Mn2+ ions in the presence TBA+, followed ion exchange initially incorporated bulkier TBA+ denser transition metals solution. resulting co-intercalated (NiCu/MnO2) catalyzed ammonia reaction (AOR) an alkaline electrolyte much lower overpotential than its Ni2+-...

The conformational landscape of the bis(fluorosulfonyl)amide, [FSI]-, anion was analyzed using data obtained from Raman spectroscopy, molecular dynamics (MD), and ab initio studies. plotting three-dimensional potential energy surfaces corresponding MD simulation conformer-population histograms show existence two stable isomers, C2 (trans) C1 (cis) conformers, confirm nature as a flexible molecule capable interconversion between conformers in liquid state. In ionic liquids, [FSI]- coexist...

Effects of the alkyl-chain length imidazolium cation on mixing state imidazolium-based ionic liquids, 1-alkyl-3-methylimidazolium (Cnmim+, lengths n 4, 6, 8, 10, and 12) bis(trifluoromethanesulfonyl)amide (TFSA−), methanol were investigated using small-angle neutron scattering (SANS), attenuated total reflectance infrared (ATR-IR), NMR techniques. SANS measurements revealed that Cnmim+TFSA− is heterogeneously mixed with in mole fraction range 0.8 ≤ xCD3OD 0.995. The heterogeneity...

The physicochemical properties (ionic conductivity, viscosity, density, and self-diffusion coefficient) of tri-n-ethylpentylphosphonium bis(trifluoromethanesulfonyl)amide (TEPP-TFSA) ionic liquid were compared with those tri-n-ethylpentylammonium (TEPA-TFSA). Compared the TEPA-TFSA liquid, density viscosity phosphorus are lower, although conductivity coefficient higher. molar conductivities for values obtained by electrochemical impedance method (electrochemical conductivity) calculated from...

The tacticity effect on phase separation process of poly(N-isopropylacrylamide) (PNiPAM) aqueous solutions was investigated by dynamic light scattering (DLS) and small angle neutron (SANS) measurements. SANS measurement revealed that hydrophobicity PNiPAM consisting meso- racemo-isomers increased with increasing the meso-content. This result is in accordance previous experimental simulation study NiPAM dimers (DNiPAM) trimers (TNiPAM) [Katsumoto, Y.; J. Phys. Chem. B 2010, 114, 13312−13318,...