Electroreduction of Chlorine Gas at Platinum Electrodes in Several Room Temperature Ionic Liquids: Evidence of Strong Adsorption on the Electrode Surface Revealed by Unusual Voltammetry in Which Currents Decrease with Increasing Voltage Scan Rates

Voltammetry is reported for chlorine, Cl-2, dissolved in various room temperature ionic liquids using platinum microdisk electrodes. A single reductive voltammetric wave is seen and attributed to the two-electron reduction of chlorine to chloride. Studies of the effect of voltage scan rate reveal uniquely unusual behavior in which the magnitude of the currents decrease with increasing scan rates. A model for this is proposed and shown to indicate the presence of strongly adsorbed species in the electrode reaction mechanism, most likely chlorine atoms, Cl*((ads)).

Formation of Ammonia during the NO-H-2 Reaction over Pt/ZrO2

The mechanism for the formation of NH3 during the NO-H-2 reaction over Pt/ZrO2 was studied. Steady-state isotopic transient kinetic analysis was carried out with isotopic switching from (NO)-N-15-D-2 to (NO)-N-14-D-2, and the results revealed that formation of N-2 and N2O was associated with linearly adsorbed NO on the Pt surface, whereas ammonia formation was associated with NDx species adsorbed on ZrO2. The adsorbed NHx species were not observed on the surface of ZrO2 during NH3 adsorption. From transient kinetic experiments, the formation rates of NHx species and of gaseous NH3 agreed with each other, suggesting that the NHx species on ZrO2 was an ammonia intermediate. The NDx species did not react with D-2 directly, but H-D exchange occurred easily. The addition of H2O to the NO-H-2 feed gas enhanced the formation of NH3. In situ diffuse reflectance spectra and transient kinetic analysis revealed that H2O enhanced the conversion of NHx species to NH3.

Green synthesis of ZnO nanoparticles in a room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Nanoparticles of ZnO with the wurtzite structure have been successfully synthesized via a microwave through the decomposition of zinc acetate dihydrate in an ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, as a solvent. Fundamental characterizations including X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were conducted for the ZnO nanostructures.

Azaarene cis-dihydrodiol-derived 2,2 '-bipyridine ligands for asymmetric allylic oxidation and cyclopropanation

Biphenyl dioxygenase-catalysed cis-dihydroxylation of 2-chloroquinoline, 2-chloro-3-methylquinoline and 2-chloro-6-phenylpyridine substrates yielded the corresponding enantiopure cis-dihydrodiols; enantiopure 2,2'-bipyridines, synthesised in four steps from 2-chloroquinoline, proved to be efficient chiral ligands in catalytic asymmetric allylic oxidation and cyclopropanation reactions of alkenes.

Chemoenzymatic synthesis of chiral 4,4 '-bipyridyls and their metal-organic frameworks

The first enantiopure 4,4'-bipyridyls, 6, 8, and 9 have been prepared in four or five steps via bacterial dioxygenase-catalysed cis-dihydroxylation of 4-chloroquinoline 1 and C-C coupling; ligands 6 and 9 are found to be effective building blocks for the preparation of chiral metal-organic frameworks as demonstrated with the rational synthesis of two pillared-grid structures [Zn-2(fumarate)(2)(L)], which exhibit interesting structural and dynamic aspects.

THEORY AND DESIGN OF A TUNABLE QUASI-LUMPED QUADRATURE COUPLER

In this article, we present the theory and a design methodology for a unable Quasi-Lumped Quadrature Coupler (QLQC). Because of its topology, the coupler is simply reconfigured by switching the bias of two varactor diodes via a very simple DC bias circuitry. No additional capacitors or inductors are required. A prototype at 3.5 GHz is etched on a 0.130-mm-thick layer substrate with a dielectric material of relative permittivity of 2.22. The simulated and measured scattering parameters are, presented. (c) 2009 Wiley Periodicals, Inc. Microwave Opt Technol Lett 51: 2219-2222 2009: Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/mop.24526

FREQUENCY SELECTIVE SURFACE WITH DUAL BAND SWITCHABLE REFLECTION AND TRANSMISSION CHARACTERISTICS

A pin diode-loaded active doubly periodic flat strip FSS is shown to act as a dynamic screen. It is shown that by means of d.c. bias control, we can utilize the screen in, (1) transmission mode as a dual band electromagnetic shutter, or with the inclusion of a ground plane in reflection mode, (is (2) it dual band refection canceller. (3) an amplitude shift keying (ASK) spatial modulator. The properties of the FSS are characterized using a specially designed parallel plate waveguide simulator that permits normal incidence excitation of the FSS under test. (C) 2009 Wiley Periodicals. Inc. Microwave Opt Technol Lett 51: 2059-2061, 2009; Published online in Wiley Inter-Science (www. interscience.wiley.com). DOI 10.1002/mop.24547

Adding value to renewables: a one pot process combining microbial cells and hydrogen transfer catalysis to utilise waste glycerol from biodiesel production

Waste glycerol was converted to secondary amines in a one pot reaction, using Clostridium butyricum and catalytic hydrogen transfer-mediated amination.

MODULATED BACKSCATTER MICROWAVE SECURITY SENSOR

A system capable of deployment as a microwave security sensor which can automatically reject background clutter is presented. The principle of operation is based on analog homodyne detection using 1. Q single side-band down conversion of an AM backscattered modulating signal envelope. A demonstrator is presented which operates with a carrier frequency of 2 GHz and 500 KHz backscattered signal. When deployed in a multipath rich open plan office environment the S/N ratio obtained at the detection output was better than 20 dB at 20 in range with 20 dBm EIRP in a 2 MHz detection bandwidth despite the presence of time varying and static clutter. (C) 2009 Wiley Periodicals, Inc. Microwave Opt Technol Lett 51: 2492-2495, 2009; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/mop.24636

EFFECT OF SURFACE RESISTOR LOADING ON HIGH-IMPEDANCE SURFACE RADAR ABSORBER RETURN LOSS AND BANDWIDTH

A simple method for the selection of the appropriate choice of surface-mounted loading resistor required for a thin radar absorber based on a high-impedance surface (HIS) principle is demonstrated. The absorber consists of a HIS, (artificial magnetic ground plane), thickness 0.03 lambda(0) surface-loaded resistive-elements interconnecting a textured surface of square patches. The properties of absorber are characterized under normal incident using a parallel plate waveguide measurement technique over the operating frequency range of 2.6-3.95 GHz. We show that for this arrangement return loss and bandwidth are insensitive to +/- 2% tolerance variations in surface resistor values about the value predicted using the method elaborated in this letter, and that better than -28 dB at 3.125 GHz reflection loss can be obtained with an effective working bandwidth of up to 11% at -10 dB reflection loss. (C) 2009 Wiley Periodicals, Inc. Microwave Opt Technol Lett 51: 1733-1775, 2009; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/mop.24454

Investigating the Mechanism and Electrode Kinetics of the Oxygen vertical bar Superoxide (O-2 vertical bar O-2(center dot-)) Couple in Various Room-Temperature Ionic Liquids at Gold and Platinum Electrodes in the Temperature Range 298-318 K

The reduction of oxygen was studied over a range of temperatures (298-318 K) in n-hexyltriethylammonium bis(trifluoromethanesulfonyl)imide, [N-6,N-2,N-2,N-2][NTf2], and 1-butyl-2,3-methylimidazolium bis(trifluoromethanesulfonyl)imide, [C(4)dmim][NTf2] on both gold and platinum microdisk electrodes, and the mechanism and electrode kinetics of the reaction investigated. Three different models were used to simulate the CVs, based on a simple electron transfer ('E'), an electron transfer coupled with a reversible homogeneous chemical step ('ECrev') and an electron transfer followed by adsorption of the reduction product ('EC(ads)'), and where appropriate, best fit parameters deduced, including the heterogeneous rate constant, formal electrode potential, transfer coefficient, and homogeneous rate constants for the ECrev mechanism, and adsorption/desorption rate constants for the EC(ads) mechanism. It was concluded from the good simulation fits on gold that a simple E process operates for the reduction of oxygen in [N-6,N-2,N-2,N-2][NTf2], and an ECrev process for [C(4)dmim][NTf2], with the chemical step involving the reversible formation of the O-2(center dot-)center dot center dot center dot [C(4)dmim](+) ion-pair. The E mechanism was found to loosely describe the reduction of oxygen in [N-6,N-2,N-2,N-2][NTf2] on platinum as the simulation fits were reasonable although not perfect, especially for the reverse wave. The electrochemical kinetics are slower on Pt, and observed broadening of the oxidation peak is likely due to the adsorption of superoxide on the electrode surface in a process more complex than simple Langmuirian. In [C(4)dmim][NTf2] the O-2(center dot-) predominantly ion-pairs with the solvent rather than adsorbs on the surface, and an ECrev quantitatively describes the reduction of oxygen on Pt also.

Remarkable stability of ionic gold supported on sulfated lanthanum oxide

Isolated cationic gold deposited on sulfated lanthanum oxide has been shown to exhibit remarkable stability opening a promising way of stabilising ionic gold for catalytic reactions.

Electrochemical Oxidation of Hydrogen Sulfide at Platinum Electrodes in Room Temperature Ionic Liquids: Evidence for Significant Accumulation of H2S at the Pt/1-Butyl-3-methylimidazolium Trifluoromethylsulfonate Interface

Electrochemical oxidation of hydrogen sulfide gas (H2S) has been studied at a platinum microelectrode (10 mu m diameter) in five room temperature ionic liquids (RTILs): [C(4)mim][OTf], [C(4)dmim][NTf2], [C(4)mim][PF6],. [C(6)mim][FAP], and [P-14,P-6,P-6,P-6][FAP] (where [C-n mim](+) = 1-alkyl-3-methylimidazolium, [C(n)dmim](+) = 1-alkyl-2,3-dimethylimidazolium, [P-14,P-6,P-6,P-6](+) = tris(p-hexyl)-tetradecylphosphonium, [OTf](-) = trifluoromethlysulfonate, [NTf2](-) = bis(trifluoromethylsulfonyl)imide, [PF6](-) = hexafluorophosphate, and [FAP](-) = trifluorotris(pentafluoroethyl)phosphate). In four of the RTILs ([C(4)dmim][NTf2], [C(4)mim][PF6], [C(6)mim][FAP], and [P-14,P-6,P-6,P-6][FAP]), no clear oxidative signal was observed. In [C(4)mim][OTf], a chemically irreversible oxidation peak was observed on the oxidative sweep with no signal seen on the reverse scan. The oxidative signal showed an adsorptive stripping peak type followed by near steady-state limiting current behavior. Potential step chronoamperometry was carried out on the reductive wave, giving a diffusion coefficient and solubility of 1.6 x 10(-11) m(2) s(-1) and 7 mM, respectively (at 25 degrees C). Using these data, we modeled the oxidation signal kinetically, assuming adsorption preceded oxidation and that adsorption was approximately Langmuirian. The oxidation step was described by an electrochemically fully irreversible Tafel law/Butler-Volmer formalism. Modeling indicated a substantial buildup of H2S in the double layer in excess of the coverage that would be expected for a monolayer of chemisorbed H2S, reflecting high solubility of the gas in [C(4)mim][OTf] and possible attractive interactions with the [OTf](-) anions accumulated at the electrode at potentials positive of the potential of zero charge. Solute enrichment of the double layer in the solution adjacent to the electrode appears a novel feature of RTIL electrochemistry.

Dissolved Argon Changes the Rate of Diffusion in Room Temperature Ionic Liquids: Effect of the Presence and Absence of Argon and Nitrogen on the Voltammetry of Ferrocene

This work explores the effects of argon and nitrogen, two electrochemically and chemically inert gases frequently used in sample preparation of room temperature ionic liquid (RTIL) solutions, on the eelectrochemical characterization of ferrocene (Fc) dissolved in the RTIL 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C(2)mim][NTf2]). Remarkably, chronoamperometrically determined diffusion coefficients of Fc in [C(2)mim][NTf2] are found to increase from 4.8 (+/- 0.2) x 10(-11) m(2) s(-1) under vacuum conditions to 6.6 (+/- 0.5) x 10(-11) m(2) s(-1) in an atmosphere of 1 atm Ar. In contrast, exposing a vacuum-purified sample to an atmosphere of 1 atm N-2 resulted in no significant change in the measured diffusion coefficient of Fc. The effect of dissolved argon on diffusion transport is unexpected and has implications in electrochemistry and elsewhere. Fc was found to volatilize under vacuum conditions. We propose, however, that evacuation of the cell by vacuum prior to electrochemical measurements being carried out is the only way to ensure that no contamination of the sample occurs, and use of an in situ method of determining the diffusion coefficient and concentration of Fc dispells,any ambiguity associated with Fc depletion by vacuum.