Ionic liquids with hydrogenated and perfluorinated chains: Structural study of the [P6,6,6,14][FnCOO] n = 7, 9, 11. Checking the existence of polar – hydrogenated – perfluorinated triphilic continuity

Silva, Gonçalo M. C.; Beira, Maria Jardim; Morgado, Pedro; Branco, Luı́s C.; Sebastião, Pedro J.; Lopes, José N. Canongia; Filipe, Eduardo J. M.

doi:10.1016/j.molliq.2022.120506

Cited by 7 publications

(8 citation statements)

References 62 publications

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“…The first question, molecular homogeneity, can be answered directly from the S/WAXS patterns. Mesoscale separation of the diluent should give rise to additional scattered intensity at low q , near or below the nanostructure SAXS prepeak, as has been observed for fluorous protic ILs that form tricontinuous structures, − and in other ternary mixtures with longer range structures. ,− However, at all TFTFE dilutions in all three ILs, the S/WAXS patterns are resiliently flat and featureless at all q below the nanostructure peak of HMIM TFSI and HMIM FAP. This means that these LCILEs cannot be described as a dispersion of IL droplets in TFTFE, or vice versa, and therefore, TFTFE is molecularly dispersed throughout the IL.…”

Section: Resultsmentioning

confidence: 54%

Nanostructure of Locally Concentrated Ionic Liquids in the Bulk and at Graphite and Gold Electrodes

Wang,

Buzolic,

Mullen

et al. 2023

ACS Nano

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The physical properties of ionic liquids (ILs) have led to intense research interest, but for many applications, high viscosity is problematic. Mixing the IL with a diluent that lowers viscosity offers a solution if the favorable IL physical properties are not compromised. Here we show that mixing an IL or IL electrolyte (ILE, an IL with dissolved metal ions) with a nonsolvating fluorous diluent produces a low viscosity mixture in which the local ion arrangements, and therefore key physical properties, are retained or enhanced. The locally concentrated ionic liquids (LCILs) examined are 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HMIM TFSI), 1hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate (HMIM FAP), or 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate (BMIM FAP) mixed with 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether (TFTFE) at 2:1, 1:1, and 1:2 (w/w) IL:TFTFE, as well as the locally concentrated ILEs (LCILEs) formed from 2:1 (w/w) HMIM TFSI−TFTFE with 0.25, 0.5, and 0.75 m lithium bis(trifluoromethylsulfonyl)imide (LiTFSI). Rheology and conductivity measurements reveal that the added TFTFE significantly reduces viscosity and increases ionic conductivity, and cyclic voltammetry (CV) reveals minimal reductions in electrochemical windows on gold and carbon electrodes. This is explained by the small-and wide-angle X-ray scattering (S/WAXS) and atomic force microscopy (AFM) data, which show that the local ion nanostructures are largely retained in LCILs and LCILEs in bulk and at gold and graphite electrodes for all potentials investigated.

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Section: Resultsmentioning

confidence: 54%

Nanostructure of Locally Concentrated Ionic Liquids in the Bulk and at Graphite and Gold Electrodes

Wang,

Buzolic,

Mullen

et al. 2023

ACS Nano

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“…The pressure and temperature were kept constant with the Parrinello-Rahman and Nosé-Hoover , barostat and thermostat, with coupling constants of 10 and 0.5 ps, respectively. Pressure was set to 1 bar, and the temperature was kept at 298.15 or 343.15 K. The algorithm for determination of aggregation has been described previously, where the cut-off distance between PPO beads was set to 0.7 nm, the first minimum of the PPO-PPO radial distribution function.…”

Section: Methodsmentioning

confidence: 99%

Using the SAFT-γ-Mie to Generate Coarse-Grained Force Fields Useable in Molecular Dynamics Simulations: Describing the Micellar Phases of Polyalkylglycols in Aqueous Solutions

Silva

Pérez‐Sánchez

Pantano

et al. 2023

Ind. Eng. Chem. Res.

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In this work, we showcase the potential of the SAFT-γ-Mie equation of state to obtain, in a top-down approach, coarse-grained molecular models capable of describing micellization phenomena. For this purpose, we selected polyethylene oxide (PEO)/polypropylene oxide (PPO) triblock copolymers in aqueous solutions as a case study. The model was fitted to reproduce the thermophysical properties�liquid densities and vapor pressures�of small PEO/PPO oligomers as well as the activity coefficients or liquid−liquid phase diagrams of their binary mixtures with water. At low concentrations, the MD simulations show the formation of spherical micelles of morphology comparable to experiments, with the characteristic star-shaped or flower-shaped morphology depending on the polymer block sequence. The local structure and molecular conformations were analyzed, showing distinctions between the two types of aggregates. At higher concentrations, depending on the co-polymer sequence, the molecules form larger micelles or coalesce into larger aggregates when signs of phase separation are observed, as expected.

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“…The Fast field cycling (FFC) relaxometry technique [99,100] has been widely used to study molecular motions of ions in ILs [45,60,[101][102][103][104][105][106][107][108][109][110][111] due to its outstanding ability to reveal information about translational and rotational dynamics in only one experiment. Although FFC-NMR is a low-resolution technique, it is possible to study dynamics of cations and anions independently if they are composed of different NMR active nuclei.…”

Section: Of 33mentioning

confidence: 99%

“…In spite of the fact that in general ILs consist of interacting non-spherical ions, the force-free-hard-sphere (FFHS) model [112,113] has been employed successfully to describe the spin-lattice relaxation due to translational diffusion in these systems [45,60,[101][102][103][104][105][106][107][108][109][110][111]115,116]. Considering that there are no previous studies that extend this diffusion model for elongated molecules, it may be considered as a very first approximation to describe the translational diffusion in ionic liquids.…”

Section: Of 33mentioning

confidence: 99%

Nuclear Magnetic Resonance Relaxation Pathways in Electrolytes for Energy Storage

Fraenza¹,

Greenbaum²,

Suarez³

2023

Preprint

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NMR spin relaxation times have been an instrumental tool in deciphering the local en-vironment of ionic species, the various interactions they engender and the effect of these interactions on their dynamics in conducting media. Of particular importance has been their application in studying the wide range of electrolytes for energy storage, on which this chapter is based. Here we highlight some of the research carried out on electrolytes in recent years using NMR relaxometry techniques. Specifically, studies on liquid electro-lytes, such as ionic liquids and organic solvent; on semi-solid-state electrolytes, such as ionogels and polymer gels, and solid electrolytes such as glasses, glass ceramics and polymers. Although this chapter focuses on a small selection of materials, we believe they demonstrate the breadth of application and the invaluable nature of NMR relaxometry.

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Ionic liquids with hydrogenated and perfluorinated chains: Structural study of the [P6,6,6,14][FnCOO] n = 7, 9, 11. Checking the existence of polar – hydrogenated – perfluorinated triphilic continuity

Cited by 7 publications

References 62 publications

Nanostructure of Locally Concentrated Ionic Liquids in the Bulk and at Graphite and Gold Electrodes

Nanostructure of Locally Concentrated Ionic Liquids in the Bulk and at Graphite and Gold Electrodes

Using the SAFT-γ-Mie to Generate Coarse-Grained Force Fields Useable in Molecular Dynamics Simulations: Describing the Micellar Phases of Polyalkylglycols in Aqueous Solutions

Nuclear Magnetic Resonance Relaxation Pathways in Electrolytes for Energy Storage

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