ALKALI AND ALKALINE-EARTH METAL-ION TRANSFER ACROSS THE LIQUID-LIQUID INTERFACE FACILITATED BY IONOPHORE ETH157

The H+, Li+, Na+, K+, Mg2+, Ca2+ and Ba2+ ion transfer across the water/nitrobenzene (NB) and water/1,2-dichloroethane (DCE) interfaces, facilitated by the ionophore ETH157, has been investigated by cyclic voltammetry (CV). The mechanism of the transfer process has been discussed, and the diffusion coefficients and the stability constants of the complexes formed in the nitrobenzene phase have been determined.

CYCLIC VOLTAMMETRIC STUDY ON THE TRANSFER MECHANISM OF ALKALI-METAL IONS ACROSS LIQUID LIQUID INTERFACE FACILITATED BY TRITON X-100

The transfer behavior of alkali motal ions K~+ and Na~+ across the interfaces of water/nitrobenzene and water/1, 2-dichloroethane facilitated by Triton X-100 is investigated by cyclic voltammetry with four electrodes. The equations of interfacial half-wave potential derived in terms of the mechanism proposed isverified by the experimental data and consistent with the practical △_0~wφ_p-pM curves.

Preparation of nanoparticulate metal catalysts in porous supports using an ionic liquid route; hydrogenation and C-C coupling

Aerogels containing palladium metal nanoparticles were prepared using an ionic liquid route and tested for activity towards hydrogenation and Heck C-C coupling reactions. (C) 2003 Elsevier B.V. All rights reserved.

Polynuclear metal complexes obtained from the task-specific ionic liquid betainium bistriflimide

The task-specific ionic liquid betainium bis(trifluoromethylsulfonyl)imide, [Hbet][Tf2N], was used to dissolve metal oxides and hydroxides. The crystal structures of the resulting metal betaine bistriflimide complexes exhibit a rich structural variety. A trimeric structure was found for the cobalt(II) compound, [Co-3(bet)(8)(Hbet)(2)(H2O)(2)][Tf2N](9)[Hbet], a tetrameric structure for the manganese(II) and zinc(II) compound, [Mn-4(bet)(10)(H2O)(4)][Tf2N](8) and [Zn-4(bet)(10)(H2O)(2)][Tf2N](8), respectively, a pentameric structure for the nickel(II) compound, [Ni-5(bet)(12)(H2O)(6)][Tf2N](10), an oxo-hydroxo-cluster formation for the lead(II) compound, [(Pb4O)Pb(OH)(bet)(8)(Tf2N)3] [Tf2N](4)center dot MeOH, and a polymeric structure for the silver(I) compound, [Ag-2(bet)(2)(Tf2N)Ag-2(bet)(2)][Tf2N](3). The zwitterionic nature of the betaine ligand and the weakly coordinating ability of the bis(trifluoromethylsulfonyl)imide [Tf2N]- anion facilitates the incorporation of metal ions into oligonuclear and polynuclear metal complexes.

Task-specific ionic liquid for solubilizing metal oxides

Protonated betaine bis(trifluoromethylsulfonyl) imide is an ionic liquid with the ability to dissolve large quantities of metal oxides. This metal-solubilizing power is selective. Soluble are oxides of the trivalent rare earths, uranium(VI) oxide, zinc(II) oxide, cadmium( II) oxide, mercury( II) oxide, nickel( II) oxide, copper(II) oxide, palladium(II) oxide, lead(II) oxide, manganese( II) oxide, and silver( I) oxide. Insoluble or very poorly soluble are iron(III), manganese(IV), and cobalt oxides, as well as aluminum oxide and silicon dioxide. The metals can be stripped from the ionic liquid by treatment of the ionic liquid with an acidic aqueous solution. After transfer of the metal ions to the aqueous phase, the ionic liquid can be recycled for reuse. Betainium bis( trifluoromethylsulfonyl) imide forms one phase with water at high temperatures, whereas phase separation occurs below 55.5 degrees C ( temperature switch behavior). The mixtures of the ionic liquid with water also show a pH-dependent phase behavior: two phases occur at low pH, whereas one phase is present under neutral or alkaline conditions. The structures, the energetics, and the charge distribution of the betaine cation and the bis( trifluoromethylsulfonyl) imide anion, as well as the cation-anion pairs, were studied by density functional theory calculations.

Alkali-metal salts of aromatic carboxylic acids: Liquid crystals without flexible chains

The alkali-metal salts of meta-substituted benzoic acids exhibit a smectic A mesophase at high temperatures. These compounds are examples of liquid crystals without terminal alkyl chains. The influence of the metal ion and of the type of substituents on the transition temperatures is discussed. Compounds with the substituent in the ortho- and para-positions are non-mesomorphic. The crystal structures of the compounds Rb(C7H4ClO2)(C7H4ClO2H), Na(C7H4IO2)(H2O), K(C7H4ClO2)(C7H4ClO2H) and Rb(C7H4BrO2)(C7H4BrO2H) have been determined by X-ray crystallography. These compounds possess a layerlike structure in the solid state. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Microwave Irradiation for the Facile Synthesis of Transition-Metal Nanoparticles (NPs) in Ionic Liquids (ILs) from Metal-Carbonyl Precursors and Ru-, Rh-, and Ir-NP/IL Dispersions as Biphasic Liquid-Liquid Hydrogenation Nanocatalysts for Cyclohexene

Stable chromium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, and iridium metal nanoparticles (MNPs) have been reproducibly obtained by facile, rapid (3 min), and energysaving 10 W microwave irradiation (MWI) under an argon atmosphere from their metal–carbonyl precursors [Mx(CO)y] in the ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]). This MWI synthesis is compared to UV-photolytic (1000 W, 15 min) or conventional thermal decomposition (180–2508C, 6–12 h) of [Mx(CO)y] in ILs. The MWIobtained nanoparticles have a very small (<5 nm) and uniform size and are prepared without any additional stabilizers or capping molecules as long-term stable M-NP/IL dispersions (characterization by transmission electron microscopy (TEM), transmission electron diffraction (TED), and dynamic light scattering (DLS)). The ruthenium, rhodium, or iridium nanoparticle/IL dispersions are highly active
and easily recyclable catalysts for the biphasic liquid–liquid hydrogenation of cyclohexene to cyclohexane with activities of up to 522 (mol product)(mol Ru)1h1 and 884 (mol product)(molRh)1h1 and give almost quantitative conversion within 2 h at 10 bar H2 and 908C. Catalyst poisoning experiments with CS2 (0.05 equiv per Ru) suggest a heterogeneous surface catalysis of RuNPs.

LIQUID MARBLES GRANULATED USING SUPER-HYDROPHOBIC METAL POWDERS

Superhydrophobic (SH) particles based on a copper substrate were prepared by a silver deposition technique of different particle sizes from 10µm to 425µm. Such SH particles were found to be pH-responsive and liquid marbles formed using the SH copper substrate destabilised under certain pH conditions. The exposure to high concentrations of acidic or basic gases caused immediate collapse of the liquid marble. However, low concentrations of acidic and basic gases could diffuse across the shell of liquid marbles without adversely affecting the structure. Liquid marbles formed with large SH particles (425
µm) did not fully form a mono-layer around the liquid droplet. This phenomenon, whereby SH particles slide down the surface of the water droplet until an equilibrium position is reached, was studied using a mathematical approach, which related the angle to the vertical axis of the SH particles at t
he equilibrium F, to the shape of liquid marble and the contact angle, ?.

Development of a heterogeneous catalyst for lignocellulosic biomass conversion:Glucose dehydration by metal chlorides in a silica-supported ionic liquid layer

An attempt is made to immobilize the homogeneous metal chloride/EMIMCl catalyst for glucose dehydration to 5-hydroxymethylfurfural. To this end, ionic liquid fragments were grafted to the surface of SBA-15 to generate a heterogenized mimick of the homogeneous reaction medium. Despite a decrease in the surface area, the ordered mesoporous structure of SBA-15 was largely retained. Metal chlorides dispersed in such ionic liquid film are able to convert glucose to HMF with much higher yields as is possible in the aqueous phase. The reactivity order CrCl > AlCl > CuCl > FeCl is similar to the order in the ionic liquid solvent, yet the selectivity are lower. The HMF yield of the most promising CrCl-Im-SBA-15 can be improved by using a HO:DMSO mixture as the reaction medium and a 2-butanol/MIBK extraction layer. Different attempts to decrease metal chloride leaching by using different solvents are described. © 2013 American Institute of Chemical Engineers Environ Prog.

High energy resolution fluorescence detection XANES - an in situ method to study the interaction of adsorbed molecules with metal catalysts in the liquid phase

The change in the Pt electronic structure following the adsorption of an a,ß-unsaturated aldehyde and ketone was followed by in situ HERFD-XANES in the liquid phase. The resulting shift in the Pt Fermi energy is in good agreement with the molecule adsorption energy trends calculated by DFT and provides insight into the reaction selectivity.

Application of permeation liquid membrane and scanned stripping chronopotentiometry to metal speciation analysis of colloidal complexes

The potential of permeation liquid membrane (PLM) to obtain dynamic metal speciation information for colloidal complexes is evaluated by measurements of lead(II) and copper(II) complexation by carboxyl modified latex nanospheres of different radii (15, 35, 40 and 65 nm). The results are compared with those obtained by a well characterized technique: stripping chronopotentiometry at scanned deposition potential (SSCP). Under the PLM conditions employed, and for large particles or macromolecular ligands, membrane diffusion is the rate-limiting step. That is, the flux is proportional to the free metal ion concentration with only a small contribution from labile complexes. In the absence of ligand aggregation in the PLM channels, good agreement was obtained between the stability constants determined by PLM and SSCP for both metals.

Predicting sizes of hexagonal and gyroid metal nanostructures from liquid crystal templating

We describe a method to predict and control the lattice parameters of hexagonal and gyroid mesoporous materials formed by liquid crystal templating. In the first part, we describe a geometric model with which the lattice parameters of different liquid crystal mesophases can be predicted as a function of their water/surfactant/oil volume fractions, based on certain geometric parameters relating to the constituent surfactant molecules. We demonstrate the application of this model to the lamellar (LR), hexagonal (H1), and gyroid bicontinuous cubic (V1) mesophases formed by the binary Brij-56 (C16EO10)/water system and the ternary Brij-56/hexadecane/water system. In this way, we demonstrate predictable and independent control over the size of the cylinders (with hexadecane) and their spacing (with water). In the second part, we produce mesoporous platinum using as templates hexagonal and gyroid phases with different compositions and show that in each case the symmetry and lattice parameter of the metal nanostructure faithfully replicate those of the liquid crystal template, which is itself in agreement with the model. This demonstrates a rational control over the geometry, size, and spacing of pores in a mesoporous metal.