Effect of nano-dispersed silica on the ion-conducting behavior of PMMA-based polymer gel electrolytes containing LiPF<Subscript>6</Subscript>

Nano-sized silica poly(methylmethacrylate)-based gel electrolyte containing lithium hexafluorophosphate (LiPF₆) was synthesized by using different binary solvent mixture (propylene carbonate(PC) and dimethylformamide (DMF) in different volume ratio). Role of DMF in PC: Higher DMF content in PC-based electrolyte shows higher ionic conductivity at all polymer content and at wide temperature regions (10-70 °C). A small increment in ionic conductivity at lower content of polymer in liquid/gel electrolyte was observed and having maximum conductivity of 13.12 mS/cm at 25 °C. Stability (mechanically and electrically), viscosity and ionic conductivity of gel electrolytes were improved with the addition of nano-sized silica at ambient temperature. Ionic conductivity of nano-sized silica-based gel electrolyte does not change much over 5^o–70 °C temperature range and is factor-wise only which make indispensable in different electrochemical devices. Also polymer gel electrolyte membranes as such and with dispersed silica nano-particles were characterized through scanning electron microscope to study the morphology of gel matrix.     

Features of spin exchange in nitroxide biradicals in the ionic liquid bmimPF<Subscript>6</Subscript>

The intramolecular electron spin exchange has been studied by electron paramagnetic resonance (EPR) spectroscopy in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF₆) for various nitroxide biradicals as a function of temperature and the nature of the connecting bridge between two >NO^· centers. Temperature variations of the isotropic nitrogen hyperfine splitting constant a and exchange integral values |J/a| were measured from EPR spectra and analyzed. Thermodynamic parameters of the conformational rearrangements were obtained. The spin exchange in rigid and flexible biradicals dissolved in the ionic liquid bmimPF₆ was compared with that in toluene solutions. Interesting features of the spin exchange in biradicals in ionic liquid were observed and explained as a result of the specific intramolecular conformational transitions. The first example of a rather rigid biradical molecule becoming flexible under the influence of an ionic liquid is reported.     

Metal-free activation of H<Subscript>2</Subscript>O<Subscript>2</Subscript> by synergic effect of ionic liquid and microwave: chemoselective oxidation of benzylic alcohols to carbonyls and unexpected formation of anthraquinone in aqueous condition

H₂O₂ mediated oxidation of alcohols in ionic liquid is revisited, wherein, ionic liquids under the influence of microwave irradiation have been found to facilitate activation of H₂O₂ without any metal catalyst in aqueous condition. The method utilizes a neutral ionic liquid [hmim]Br both as catalyst and solvent for efficient and chemoselective oxidation of benzyl alcohol derivatives on aromatic (β, γ) alcohols, cyclic and aliphatic analogues, which can be a useful synthetic approach in total synthesis of complex organic compounds/natural products. Moreover, an unexpected oxidation of 9-anthracenyl propanol, a polyaromatic benzyl alcohol, resulting in the formation of 9,10-anthraquinone by the loss of propyl side chain was observed. Plausible mechanism and further exploration of this method on various other related substrates are discussed in detail.     

新型离子液体预富集-石墨炉原子吸收法测定透析液中超痕量铅

设计合成了新型室温离子液体—1-丁基-3-三甲基硅烷咪唑六氟磷酸,并用于透析液中超痕量铅的预富集。从双硫腙作为螯合剂使透析液(1 000 mL或更大体积)中存在的铅(Ⅱ)形成中性的铅-双硫腙配合物,摒弃传统的有机萃取剂—四氯化碳,代以1-丁基-3-三甲基硅烷咪唑六氟磷酸为绿色萃取剂来萃取铅配合物。收集含有配合物的下层离子液体相,加入硝酸分解铅配合物从而使铅(Ⅱ)进入水相,其水溶液中的铅含量直接用石墨炉原子吸收法测定。实验表明此富集体系明显优于传统有机溶剂四氯化碳和经典离子液体1-丁基-3-甲基咪唑六氟磷酸萃取体,铅的一次萃取率和富集倍数分别在99%和200以上。预富集结合石墨炉原子吸收法应用于透析液中超痕量铅的测定,结果令人满意。     

Changes in dynamical behavior of ionic liquid in silica nano-pores

Dielectric relaxation measurement has been carried out on an ionic liquid (1-butyl-3-methyl imidazolium hexafluorophosphate, [BMIM][PF₆]) confined in nano-porous silica matrix. Two dielectric relaxation peaks have been observed in the confined ionic liquid (IL) while there is only one relaxation peak for bulk IL. Confinement results in layering of some IL molecules near the pore wall while other molecules, less affected by pore wall interaction, remain in the central core. The two relaxation peaks are assigned to the different dynamical behaviors of the central core and layered IL molecules.     

Structural,thermal and ion transport studies on nanocomposite polymer electrolyte-{(PEO + SiO<Subscript>2</Subscript>):NH<Subscript>4</Subscript>SCN} system

Development and characterisation of polyethylene oxide (PEO)-based nanocomposite polymer electrolytes comprising of (PEO-SiO₂): NH₄SCN is reported. For synthesis of the said electrolyte, polyethylene oxide has been taken as polymer host and NH₄SCN as an ionic charge supplier. Sol–gel-derived silica powder of nano dimension has been used as ceramic filler for development of nanocomposite electrolytes. The maximum conductivity of electrolyte ∼2.0 × 10⁻⁶ S/cm is observed for samples containing 30 wt.% silica. The temperature dependence of conductivity seems to follow an Arrhenius-type, thermally activated process over a limited temperature range.     

A piperidinium-based ester-functionalized ionic liquid as electrolytes in Li/LiFePO<Subscript>4</Subscript> batteries

A new functionalized ionic liquid (IL) based on cyclic quaternary ammonium cations with ester group and bis(trifluoromethanesulfonyl)imide ([TFSI]^?) anion, namely, N-methyl-N-methoxycarbonylpiperidinium bis(trifluoromethanesulfonyl)imide ([MMOCPip][TFSI]), was synthesized and characterized. Physical and electrochemical properties, including Li-ion transference number, ionic conductivity, and electrochemical stability, were investigated. The electrochemical window of [MMOCPip][TFSI] was 6 V, which was wide enough to be used as a common electrolyte material. The Li-ion transference number of this IL electrolyte containing 0.1 M LiTFSI was 0.56. The half-cell tests indicated that the [MMOCPip][TFSI] obviously improved the cyclability of a Li/LiFePO₄ cell. For the Li/LiFePO₄ half-cells, after 20 cycles at room temperature at 0.1 C, the discharge capacity was 109.7 mAh g^?1 with 98.7% capacity retention in the [MMOCPip][TFSI]/0.1 M LiTFSI electrolyte. The good electrochemical performance demonstrated that the [MMOCPip][TFSI] could be used as electrolyte for lithium-ion batteries.     

Synthesis and characterization of double –SO3H functionalized Brönsted acidic hydrogensulfate ionic liquid confined with silica through sol-gel method

Imidazolium-based metal and halogen-free Brönsted acidic ionic liquid (BAIL) (3,3′-(hexane-1,6-diyl)bis(2-methyl-1-(3-sulfopropyl)-1H-benzimidazolium) hydrogensulfate [HbMBIM-PS][HSO₄] was synthesized. The physicochemical properties of this BAIL were investigated using a variety of different analytical and spectroscopic techniques such as ¹H and¹³C-NMR, FT-IR, mass, UV–vis and TGA spectra. A porous silica matrix has been synthesized using BAIL and tetraethoxysilane (TEOS) as silica source by nonhydrolytic sol–gel method. The properties of IL confined silica gel matrix have been studied using FTIR, TGA, SEM, N₂-sorption measurement (BET characterization for determining pore parameters), and NH₃-TPD techniques. From the N₂-sorption measurement, it has been found that BET surface area decreased while pore volume, average pore size and porosity decreased. The thermal stability of the IL has been found to increase upon confinement in silica gel matrix. The results suggested that IL had been successfully confined on silica gel. This IL confined silica gel catalyst is environment friendly and useful for alkane isomerization and esterification reactions.     

Fabrication and electrochemical property modification of mixed matrix heterogeneous cation exchange membranes filled with Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/PAA core-shell nanoparticles

In the current research, iron oxide nanoparticles were functionalized by acrylic acid polymerization. The Fe₃O₄/PAA core-shell nanoparticles were utilized for the modification of cation exchange membranes. Ion exchange membranes were prepared by solution casting technique using cation exchange resin powder as functional group agent and tetrahydrofuran as solvent. FTIR analysis proved the formation of PAA on nanoparticles. The SOM images also showed uniform particle distribution for the prepared membrane relatively. The membrane water content was declined from 30 to 17 % by increase of nanoparticle content ratio in membrane matrix. The contact angle measurements showed that membrane surface hydrophilicity was improved by utilizing of nanoparticles in the membrane matrix. The membrane potential, permselectivity, and transport number were improved initially by increase of nanoparticle concentration in the casting solution and then began to decrease by more additive concentration. Membrane ionic flux and permeability were enhanced initially by increase of nanoparticle loading ratio up to 0.5 %wt in membrane matrix and then showed decreasing trend by more increase of nanoparticle concentration from 0.5 to 4 %wt. Membrane areal electrical resistance was decreased sharply by utilization of nanoparticles up to 0.5 %wt in membrane matrix then began to increase by more additive concentration. The prepared membranes exhibited superior selectivity and low ionic flux at neutral condition compared to other acidic and alkaline environments.     

Synthesis and characterization of silica-gold core-shell (SiO<Subscript>2</Subscript>@Au) nanoparticles

This paper reports a systematic investigation of the growth and attachment of small gold nanoparticles to the functionalized surface of larger silica nanoparticles by three different methods. Nearly monodispersed silica particles and gold nanoparticles were prepared by sol-gel method. The size of the particle could be altered by changing the concentration of reactants, temperature and the time for which they react. The nanocoreshell particles prepared by three different methods were studied using scanning electron microscopy (SEM), UV-vis spectroscopy and Fourier transform infrared spectroscopy. We have found that the third method (c), a combination of the first two methods (a) and (b), has given better results.      

Mesoporous Hybrid Materials by Simultaneous Pseudomorphic Transformation and Functionalization of Silica Microspheres

Non‐agglomerated amino‐functionalized mesoporous silica microspheres are synthesized by a one‐pot synthesis from a parent silica material. Narrow pore size distributions in the range from 3 to 5 nm are obtained with alkyltrimethylammonium structure‐directing agents (SDAs). By following the pseudomorphic transformation pathway, the particle size distribution and spherical morphology of the parent silica are retained during the synthesis. The products contain accessible and uniformly distributed amino groups. The average pore size and the ratio of small uniform mesopores (<5 nm) to larger mesopores and macropores can be controlled by choosing the appropriate SDA and by adjusting the concentration of the amino‐functionalized alkoxysilane precursor, leading to a variety of meso‐macroporous hybrid materials.     

Properties of a composite material based on multi-walled carbon nanotubes and an ionic liquid

A solid-phase composite material based on multi-walled carbon nanotubes and an ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate) has been synthesized. It has been found using infrared spectroscopy that vibrational modes of the ionic liquid are shifted by 4–12 cm^?1 toward lower energies with respect to those observed in the initial fluid due to the interaction of ionic liquid molecules with the nanotubes. Electron microscopy has revealed that, in the composite, the ionic liquid is present on the surface of nanotubes and partially inside them. It has been shown that the degree of extraction of lanthanides from aqueous solutions with the use of the synthesized composite increases with increasing content of the ionic liquid in it.     

Influence of the preparation method on the morphology of templated NiCo<Subscript>2</Subscript>O<Subscript>4</Subscript> spinel

The synthesis of NiCo₂O₄ spinel by several nanocasting strategies (i.e., multi-step nanocasting, one-step nanocasting and soft-templating), in which nickel and cobalt nitrates are used as precursors and Pluronic P123 as surfactant, is explored. First, in the multi-step nanocasting, the effect of the impregnation method (evaporation, solid–liquid and two-solvent) of the SBA-15 silica template on the morphology of NiCo₂O₄ replica is investigated. The evaporation method seems to be the best choice to obtain mesoporous NiCo₂O₄ powder which, after calcination at 375 °C and subsequent template removal, displays the highest surface area (93.1 m²/g). We have also checked the feasibility of the one-step nanoscating approach for the synthesis of ordered NiCo₂O₄ arrays, though this methodology entails severe difficulties, mainly related to the different decomposition temperature of the nitrate precursors and the P123 surfactant. Finally, randomly oriented, aggregated NiCo₂O₄ nanoparticles are obtained by means of P123 surfactant-assisted soft-templating approach.     

Synthesis, characterisation and functionalisation of luminescent silica nanoparticles

The synthesis of highly monodispersed, homogeneous and stable luminescent silica nanoparticles, synthesized using a process based on the Stöber method is reported here. These particles have been functionalised with the ruthenium and europium complexes: bis (2,2??-bipyridine)-(5-aminophenanthroline) Ru bis (hexafluorophosphate), abbreviated to (Ru(bpy)₂(phen-5-NH₂)(PF₆)), and tris (dibenzoylmethane)-mono (5-aminophenanthroline) europium(III), abbreviated to (Eu:TDMAP). Both dyes have a free amino group available, facilitating the covalent conjugation of the dyes inside the silica matrix. Due to the covalent bond between the dyes and the silica, no dye leaching or nanoparticle diameter modification was observed. The generic and versatile nature of the synthesis process was demonstrated via the synthesis of both europium and ruthenium-functionalised nanoparticles. Following this, the main emphasis of the study was the characterisation of the luminescence of the ruthenium-functionalised silica nanoparticles, in particular, as a function of surface carboxyl or amino group functionalisation. It was demonstrated that the luminescence of the ruthenium dye is highly affected by the ionic environment at the surface of the nanoparticle, and that these effects can be counteracted by encapsulating the ruthenium-functionalised nanoparticles in a plain 15 nm silica layer. Moreover, the ruthenium-functionalised silica nanoparticles showed high relative brightness compared to the free dye in solution and efficient functionalisation with amino or carboxyl groups. Due to their ease of fabrication and attractive characteristics, the ruthenium-functionalised silica nanoparticles described here have the potential to be highly desirable fluorescent labels, particularly, for biological applications.     

Templated electrodeposition of silver nanowires in a nanoporous polycarbonate membrane from a nonaqueous ionic liquid electrolyte

Template electrodeposition has been used to prepare a wide range of nanostructures but has generally been restricted to aqueous electrolytes. We report the deposition of silver nanowires in a commercial nuclear track-etched polycarbonate template from the nonaqueous ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]) using silver electrochemically dissolved from the anode. Transmission electron microscopy (TEM) shows that the nanowires have a very high aspect ratio with an average diameter of 80 nm and length of 5 μm. Ionic liquid electrolytes should greatly extend the range of metals that can be electrodeposited as nanowires using templates. PACS 81.15.Pq; 81.07.-b     

Synthesis and nanostructural investigation of TiO<Subscript>2</Subscript> nanorods doped by SiO<Subscript>2</Subscript>

TiO₂ Nano rods can be used as dye-sensitized solar cells, various sensors and photocatalysts. These nanorods are synthesized by a hydrothermal corrosion process in NaOH solution at 200°C using TiO₂ powder as the source material. In the present work, the synthesis of TiO₂ nanorods in anatase, rutile and Ti₇O₁₃ phases and synthesis of TiO₂ nanorods by incorporating SiO₂ dopant, using the sol–gel method and alkaline corrosion are reported. The morphologies and crystal structures of the TiO₂ nanorods are characterized using field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD) study. The obtained results show not only an aggregation structure at high calcination temperatures with spherical particles but also Ti–O–Si bonds having four-fold coordination with oxygen in SiO^4 −.     

Volumetric, acoustic and spectroscopic studies for binary mixtures of ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate) with alkoxyalkanols at T = (288.15 to 318.15) K

Densities and speeds of sound have been measured for the binary mixtures of ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF₆] with ethylene glycol monoethyl ether (EGMEE), diethylene glycol monoethyl ether (Di-EGMEE), triethylene glycol monoethyl ether (Tri-EGMEE) over the whole composition range at atmospheric pressure. Experimental densities have been used to estimate excess molar volumes, V^E. Changes in isentropic compressibility, Δκ_s have been estimated by using experimental speed of sound and density values. Excess properties were fitted to the Redlich-Kister polynomial equation to obtain the binary coefficients and the standard errors. The molecular scale interactions between ionic liquid and alkoxyalkanols have been investigated through ¹H NMR spectroscopy. NMR chemical shifts for hydroxyl group of alkoxyalkanols and their deviations show hydrogen bonding interactions of varying strengths between ionic liquid and alkoxyalkanol in their binary mixtures.     

Effect of molecular weight of PMMA on the conductivity and viscosity behavior of polymer gel electrolytes containing NH<Subscript>4</Subscript>CF<Subscript>3</Subscript>SO<Subscript>3</Subscript>

The addition of polymethyl methacrylate (PMMA) having different molecular weights to electrolytes containing ammonium trifluoromethanesulfonate (NH₄CF₃SO₃) in diethyl carbonate (DEC) has been found to result in conductivity enhancement and to yield gel electrolytes with conductivity higher than the corresponding liquid electrolytes. The increase in conductivity has been found to be due to the dissociation of undissociated NH₄CF₃SO₃ and ion aggregates present in the electrolytes, and this has been supported by Fourier transform infrared spectroscopy results, which suggests active interaction of PMMA and NH₄CF₃SO₃ in these gel electrolytes. The increase in conductivity also depends upon the molecular weight of the polymer used and is relatively more for PMMA having lower molecular weight. The increase in viscosity with PMMA addition also depends upon the molecular weight of the polymer and is closely related to the conductivity behavior of these electrolytes. Polymer gel electrolytes have been found to be thermally stable up to a temperature of 125 °C.     

Mesoporous Silica Materials Synthesized via Sol-Gel Methods Modified with Ionic Liquid and Surfactant Molecules

采用离子液体1-甲基-3-丁基咪唑四氟硼酸盐改性的溶胶-凝胶法以及表面活性剂十六烷基三甲基溴化铵进一步改性的溶胶-凝胶法制备介孔二氧化硅. 通过X射线衍射、氮气吸附脱附和扫描电子显微镜对所制备的样品进行表征. 结果表明,与仅用离子液体为模板制备的介孔二氧化硅相比,采用表面活性剂和离子液体的混合物为模板制备的介孔二氧化硅具有较小的孔径和较规则的孔结构. 说明利用该方法制备介孔二氧化硅,表面活性剂的加入会在一定程度上影响所制介孔二氧化硅的微结构.     

Comparison of Eu(NO<Subscript>3</Subscript>)<Subscript>3</Subscript> and Eu(acac)<Subscript>3</Subscript> precursors for doping luminescent silica nanoparticles

In this study, we report the comparison between Eu³⁺-doped silica nanoparticles synthesized by Stöber method using Eu(NO₃)₃ or Eu(acac)₃ as precursors. The impact of different europium species on the properties of the final silica nanospheres is investigated in details in terms of size, morphology, reachable doping amount, and luminescence efficiency. Moreover, the results obtained for different thermal treatments are presented and discussed. It is shown that the organic complex modify the silica growing process, leading to bigger and irregular nanoparticles (500–800 nm) with respect to the perfectly spherical ones (400 nm) obtained by the nitrate salt, but their luminescence intensity and lifetime is significantly higher when 800–900 °C annealing is performed.