Search Results (11)

While hundreds of complexes of the general formula [Ni(η⁵-C₅H₅)(NHC)(X)] exist (NHC = a N-heterocyclic carbene, X = Cl, Br, I), none is yet known with X = F. We attempted to prepare such a species by reacting nickelocene with imidazolium fluorides. Three imidazolium fluorides (ImH)⁺ F⁻ [Im = (N,N′-bis-(R)-imidazolium: 1a, IMe, R = Me; 1b, IMes, R = 2,4,6-trimethylphenyl; 1c, IPr, R = 2,6-diisopropylphenyl)] were prepared and characterized by spectroscopic methods. In addition, the salts 1b [(IMesH)⁺ F⁻] and 1c [(IPrH)⁺ F⁻] were subjected single-crystal X-ray diffraction experiments. The reactions of these imidazolium fluorides with nickelocene did not lead to [Ni(η⁵-C₅H₅)(NHC)(F)] species. Instead, the reaction of 1a [(IMeH)⁺ F⁻] and 1b [(IMesH)⁺ F⁻] with nickelocene led to the salt 2 [Ni(η⁵-C₅H₅)(IMe)₂]⁺ F⁻ and to the square planar complex 3atrans-[NiF₂(IMes)₂] respectively. Both complexes were characterized spectroscopically and by single crystal X-ray diffraction. All four X-ray diffraction studies reveal hydrogen bonding and hydrogen interactions with the F atom or anion, and in some cases with solvent molecules of crystallization, and these phenomena are all discussed. Complex 2, in particular, exhibited a wide range of interesting H-bonded interactions in the solid state. Complexes 2 and 3a were tested as catalysts for Suzuki–Miyaura coupling but were not promising: complex 2 was inactive, and while 3a did indeed catalyze the reaction, it gave widely diverging results owing to its instability in solution. Full article

Natural astaxanthin has been widely used in the food, cosmetic, and medicine industries due to its exceptional biological activity. Shrimp shell is one of the primary natural biological sources of astaxanthin. However, after astaxanthin recovery, there is still a lot of chitin contained in the residues. In this study, the residue from shrimp (Penaeus vannamei) shells after astaxanthin extraction using ionic liquid (IL) 1-ethyl-3-methyl-imidazolium acetate ([Emim]Ac) was used as a bioadsorbent to remove fluoride from the aqueous solution. The results show the IL extraction conditions, including the solid/liquid ratio, temperature, time, and particle size, all played important roles in the removal of fluoride by the shrimp shell residue. The shrimp shells treated using [Emim]Ac at 100 °C for 2 h exhibited an obvious porous structure, and the porosity showed a positive linear correlation with defluorination (D_F, %). Moreover, the adsorption process of fluoride was nonspontaneous and endothermic, which fits well with both the pseudo-second-order and Langmuir models. The maximum adsorption capacity calculated according to the Langmuir model is 3.29 mg/g, which is better than most bioadsorbents. This study provides a low-cost and efficient method for the preparation of adsorbents from shrimp processing waste to remove fluoride from wastewater. Full article

A solid-state polymer electrolyte membrane is formed by blending poly(vinylidene fluoride-co-hexafluoropropylene) with the synthesized copolymer of poly(methyl methacrylate-co-1-vinyl-3-butyl-imidazolium bis(trifluoromethanesulfonyl)imide, in which lithium bis(trifluoromethane)sulfonimide molecules are applied as the source of lithium ions. The accordingly formed membrane that contains 14 wt.% of P(MMA-co-VBIm-TFSI), 56 wt.% of PVDF-HFP, and 30 wt.% of LiTFSI manifests the best electrochemical properties, achieving an ionic conductivity of 1.11 × 10⁻⁴ S·cm⁻¹ at 30 °C and 4.26 × 10⁻⁴ S·cm⁻¹ at 80 °C, a Li-ion transference number of 0.36, and a wide electrochemical stability window of 4.7 V (vs. Li/Li⁺). The thus-assembled all-solid-state lithium-ion battery of LiFePO₄/SPE/Li delivers a discharge specific capacity of 148 mAh·g⁻¹ in the initial charge–discharge cycle at 0.1 C under 60 °C. The capacity retention of the cell is 95.2% after 50 cycles at 0.1 C and the Coulombic efficiency remains close to 100% during the cycling process. Full article

Two types of poly(5-phenyl-2-norbornene) were synthesized via ring opening metathesis and addition polymerization. The polymers sulfonation reaction under homogeneous conditions resulted in ionomer with high sulfonation degree up to 79% (IEC 3.36 meq/g). The prepared ionomer was characterized by DSC, GPC, ¹H NMR and FT-IR. Polymers for electromechanical applications soluble in common polar organic solvents were obtained by replacing proton of sulfonic group with imidazolium and 1-methylimidazlium. Membranes were prepared using the above-mentioned polymers and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4), as well as mixtures with polyvinylidene fluoride (PVDF). Mechanical, morphological, and conductive properties of the membranes were examined by tensile testing, SEM, and impedance spectroscopy, respectively. Dry and air-stable actuators with electrodes based on SWCNT were fabricated via hot-pressing. Actuators with membranes based on methylimidazolium containing ionomers outperformed classical bucky gel actuator and demonstrated high strain (up to 1.14%) and generated stress (up to 1.21 MPa) under low voltage of 2 V. Full article

Thermal treatment conditions of solid polymer polymer electrolyte (SPE) were studied with respect to their impact on the surface morphology, phase composition and chemical composition of an imidazolium ionic-liquid-based SPE, namely PVDF/NMP/[EMIM][TFSI] electrolyte. These investigations were done using scanning electron microscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry as well as X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectroscopy. A thoroughly mixed blend of polymer matrix, ionic liquid and solvent was deposited on a ceramic substrate and was kept at a certain temperature for a specific time in order to achieve varying crystallinity. The morphology of all the electrolytes consists of spherulites whose average diameter increases with solvent evaporation rate. Raman mapping shows that these spherulites have a semicrystalline structure and the area between them is an amorphous region. Analysis of FTIR spectra as well as Raman spectroscopy showed that the β-phase becomes dominant over other phases, while DSC technique indicated decrease of crystallinity as the solvent evaporation rate increases. XPS and ToF-SIMS indicated that the chemical composition of the surface of the SPE samples with the highest solvent evaporation rate approaches the composition of the ionic liquid. Full article

Poly(vinylidene fluoride) (PVDF) is a versatile thermoplastic fluoropolymer with intriguing characteristics, which is receiving considerable attention from researchers in many areas. Recently, PVDF and its copolymer, such as poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) have been blended with ionic liquids to produce blend and composite materials for target applications. In this succinct review, two types of ionic liquids that are utilized for the preparation of PVDF and PVDF-HFP blends and composites, namely, hydrophilic and hydrophobic imidazolium-based ionic liquids, are reviewed. In addition, the effect of the ionic liquids on the physicochemical properties of the PVDF and PVDF-HFP blends and composites, is described as well. On top of that, a multitude of applications of the blends and composites are also succinctly reviewed. This review may give inspirations to the polymer blend and composite researchers in diversifying the applications of thermoplastic fluoropolymers through the utilization of ionic liquids. Full article

The nanoscale ion ordering of ionic liquids at confined interfaces under high pressures was investigated in this study. 1-Hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([HMIM][NTf₂])/poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-co-HFP) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf₂])/PVdF-co-HFP were prepared and characterized by using high-pressure infrared spectroscopy. Under ambient pressure, imidazolium C²–H and C^4,5–H absorptions were blue-shifted in frequency due to the presence of PVdF-co-HFP. However, the absorption of anionic ν_a SO₂ did not reveal any significant shifts in frequency upon dilution by PVdF-co-HFP. The experimental results suggest that PVdF-co-HFP disturbs the local structures of the imidazolium C–H groups instead of the anionic SO₂ groups. The frequency shifts of C^4,5–H became dramatic for the mixtures at high pressures. These results suggest that pressure-enhanced ionic liquid–polymer interactions may play an appreciable role in IL-PVdF-co-HFP systems under high pressures. The pressure-induced blue-shifts due to the PVdF-co-HFP additions were more obvious for the [HMIM][NTf₂] mixtures than for [EMIM][NTf₂] mixtures. Full article

Smart and soft electroactive polymer actuators as building blocks for soft robotics have many beneficial properties that could make them useful in future biomimetic and biomedical applications. Gelatin—a material exploited for medical applications—can be used to make a fully biologically benign soft electroactive polymer actuator that provides high performance and has been shown to be harmless. In our study, these polypyrrole-gelatin trilayer actuators with choline acetate and choline isobutyrate showed the highest strain difference and highest efficiency in strain difference to charge density ratios compared to a reference system containing imidazolium-based ionic liquid and a traditional polyvinylidene fluoride (PVdF) membrane material. As neither the relative ion sizes nor the measured parameters of the ionic liquids could explain their behavior in the actuators, molecular dynamics simulations and density functional theory calculations were conducted. Strong cation-cation clustering was found and the radial distribution functions provided further insight into the topic, showing that the cation-cation correlation peak height is a good predictor of strain difference of the actuators. Full article

Dynamic tribochemical processes for dicationic ionic liquid containing a geminal imidazolium cation head group bridged by a poly(ethylene glycol) and a bis(trifluoromethylsulfonyl)imide anion were studied using time-resolved mechanically stimulated gas emission mass-spectrometry (MSGE-MS). In comparison with similar monocationic imidazolium ionic liquids with short alkyl or long polyether side chains, the dicationic ionic liquid had a lower coefficient of friction on Ti6Al4V alloy and smoother behavior. The analysis of volatile decomposition products suggested multiple tribochemical reactions in which both anionic and cationic moieties are involved. The tribochemical degradation of cations was mainly through the detachment of the side and bridging chains from the imidazolium head groups. The absence of volatile products containing nitrogen implies that the imidazole group remained unchanged. Hydrogen and water desorption were attributed to the reactions of hydrogen fluoride being a product of anion degradation with titanium and titanium oxide, respectively. Full article

Gel Polymer Electrolytes (GPEs) composed by ZnTf₂ salt, poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP), and different ionic liquids are synthesized using n-methyl-2-pyrrolidone (NMP) as solvent. Three different imidazolium-based ionic liquids containing diverse cations and anions have been explored. Structural and electrical properties of the GPEs varying the ZnTf₂ concentration are analyzed by ATR-FTIR, DSC, TG, and cyclic voltammetry. Free salt IL-GPEs present distinct behavior because they are influenced by the different IL cations and anions composition. However, inclusion of ZnTf₂ salt inside the polymers provide GPEs with very similar characteristics, pointing out that ionic transport properties are principally caused by Zn²⁺ and triflate movement. Whatever the IL used, the presence of NMP solvent inside the polymer’s matrix turns out to be a key factor for improving the Zn²⁺ transport inside the GPE due to the interaction between Zn²⁺ cations and carbonyl groups of the NMP. High values of ionic conductivity, low activation energy values, and good voltammetric reversibility obtained regardless of the ionic liquid used enable these GPEs to be applied in Zn batteries. Capacities of 110–120 mAh·g⁻¹ have been obtained for Zn/IL-GPE/MnO₂ batteries discharged at −1 mA·cm⁻². Full article

Current research on room-temperature ionic liquids as lubricants is described. Ionic liquids possess excellent properties such as non-volatility, non-flammability, and thermo-oxidative stability. The potential use of ionic liquids as lubricants was first proposed in 2001 and approximately 70 articles pertaining to fundamental research on ionic liquids have been published through May 2009. A large majority of the cations examined in this area are derived from 1,3-dialkylimidazolium, with a higher alkyl group on the imidazolium cation being beneficial for good lubrication, while it reduces the thermo-oxidative stability. Hydrophobic anions provide both good lubricity and significant thermo-oxidative stability. The anions decompose through a tribochemical reaction to generate metal fluoride on the rubbed surface. Additive technology to improve lubricity is also explained. An introduction to tribology as an interdisciplinary field of lubrication is also provided. Full article