The electrochemical oxidation and reduction of nitrate ions in the room temperature ionic liquid [C(2)mim][NTf2]; the latter behaves as a 'melt' rather than an 'organic solvent'

The electrochemical oxidation of 1-butyl-3-methylimidazolium nitrate [C(4)mim][NO3] was studied by cyclic voltammetry in the room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [C(2)mim][NTf2]. A sharp peak was observed on a Pt microelectrode (d = 10 mu m), and a diffusion coefficient at infinite dilution of ca. 2.0 x 10(-11) m(2) s(-1) was obtained. Next, the cyclic voltammetry of sodium nitrate (NaNO3) and potassium nitrate (KNO3) was studied, by dissolving small amounts of solid into the RTIL [ C2mim][ NTf2]. Similar oxidation peaks were observed, revealing diffusion coefficients of ca. 8.8 and 9.0 x 10(-12) m(2) s(-1) and solubilities of 11.9 and 10.8 mM for NaNO3 and KNO3, respectively. The smaller diffusion coefficients for NaNO3 and KNO3 (compared to [C(4)mim][NO3]) may indicate that NO3- is ion-paired with Na+ or K+. This work may have applications in the electroanalytical determination of nitrate in RTIL solutions. Furthermore, a reduction feature was observed for both NaNO3 and KNO3, with additional anodic peaks indicating the formation of oxides, peroxides, superoxides and nitrites. This behaviour is surprisingly similar to that obtained from melts of NaNO3 and KNO3 at high temperatures ( ca. 350 - 500 degrees C), and this observation could significantly simplify experimental conditions required to investigate these compounds. We then used X-ray photoelectron spectroscopy (XPS) to suggest that disodium( I) oxide (Na2O), which has found use as a storage compound for hydrogen, was deposited on a Pt electrode surface following the reduction of NaNO3.

Using XPS to determine solute solubility in room temperature ionic liquids

X-Ray Photoelectron Spectroscopy (XPS) was used to quantify the amount of bromide ions present in two samples of [C(4)mpyrr]Br dissolved in the room temperature ionic liquid (RTIL) [C(4)mpyrr][N(Tf)(2)]. One sample was of a known concentration (0.436 Br atom%); the other was a saturated solution. The results obtained from quantitative XPS analysis indicated that the saturated sample had a concentration, or solubility, of 0.90 Br atom% (746 mM) at 298 K, which was then independently confirmed by potential-step chronoamperometry of the same solution.

Dynamic resonances and tunnelling in the multiphoton ionization of argon

We present results of wavepacket simulations for multiphoton ionization in argon. A single active electron model is applied to estimate the single-electron ionization rates and photoelectron energy distributions for lambda = 390 nm light with intensities up to I = 2 x 10(14) W cm(-2). The multiphoton ionization rates are compared with R-matrix Floquet calculations and found to be in very good agreement. The photoelectron energy distribution is used to study the nature of ionization at the higher intensities. Our results are consistent with recent calculations and experiments which show the imprint of the tunnelling process in the multiphoton regime. For few-cycle intense pulses, we find that the strong modulation of intensity and increased bandwidth leads to dynamic mixing of the 3d and 5s resonances.

An experiment for two-color photoionization using high intensity extreme-UNT free electron and near-IR laser pulses

We describe an experimental system designed for single-shot photoelectron spectroscopy on free atoms and molecules at the Free Electron Laser in Hamburg (FLASH at DESY). The combination of the extreme ultra-violet (EUV) Free Electron Laser and a temporally synchronized optical fs laser (Ti:Sapphire) enables a variety of two-color pump-probe experiments. The spectral, temporal and spatial characteristics of both the EUV FEL and the optical laser pulses, the experimental procedure to control their overlap as well as the performance of an electron spectrometer used to obtain single-shot photoelectron spectra are discussed. As an illustration of the capabilities of this set-up, some results on two-photon two-color ionization of rare gases are presented. (c) 2007 Elsevier B.V. All rights reserved.

The Co-Entrapment of a Homogeneous Catalyst and an Ionic Liquid by a Sol-gel Method: Recyclable Ionogel Hydrogenation Catalysts

Molecular hydrogenation catalysts have been co-entrapped with the ionic liquid [Bmim]NTf(2) inside a silica matrix by a sot-gel method. These catalytic ionogels have been compared to simple catalyst-doped glasses, the parent homogeneous catalysts, commercial heterogeneous catalysts, and Rh-doped mesoporous silica. The most active ionogel has been characterised by transmission electron microscopy, X-ray photoelectron spectroscopy, and solid state NMR before and after catalysis. The ionogel catalysts were found to be remarkably active, recyclable and resistant to chemical change.

Highly resolved absolute cross-sections for dissociative electron attachment to SF5CF3

Using two complementary experimental methods, we have measured partial (mass-resolved) cross-sections for dissociative electron attachment to the molecule trifluoromethyl sulfurpentafluoride (SF5CF3) at the gas temperature T-G = 300 K over a broad range of electron energies (E = 0.001-12 eV). The absolute scale for these cross-sections was obtained with reference to the thermal (T = 300 K) rate coefficient for anion formation (8.0(3) x 10(-8) cm(3) s(-1)). Below 1 eV, SF5- is the dominant product anion and formed through the lowest anion state which cuts the neutral SF5CF3 potential close to the S-C equilibrium distance. The highly resolved laser photoelectron attachment data exhibit a downward Wigner cusp at 86meV, indicating that the nu(4)(alpha(1)) vibrational mode is important for the primary attachment dynamics. Both SF5- and F- anions are formed with similar yields through the first excited resonance located near 3.6eV. Towards higher energies, the anions CF3-, SF4-, and SF3- are also produced. Summation of the partial cross-sections yields a total absolute cross-section for anion formation over the energy range 0.001-12 eV. This is used to calculate the dependence of the rate coefficient for dissociative electron attachment over a broad range of electron temperatures for the fixed gas temperature T-G = 300 K; good agreement is found between the calculated values and those obtained in a drift tube experiment. In addition to the experimental work, semiempirical R-matrix calculations have been Carried out for the energy dependence of the cross-section for SF5- formation. The experimental findings are semi-quantitatively recovered. (C) 2008 Elsevier B.V. All rights reserved.

Low-energy electron attachment to chloroform (CHCl3) molecules: A joint experimental and theoretical study

Results from a joint experimental and theoretical study of electron attachment to chloroform (CHCl3) molecules in the gas phase are reported. In an electron swarm study involving a pulsed Townsend technique with equal gas and electron temperatures, accurate attachment rate coefficients were determined over the temperature range 295-373 K; they show an Arrhenius-type rise with increasing temperature, corresponding to an activation energy of 0.11 (1) eV. In a high resolution electron beam experiment involving two versions of the laser photoelectron attachment method, the relative cross section for Cl- formation from CHCl3 over the energy range 0.001-1.25 eV at the gas temperature T-G = 300 K was measured. It exhibits clear downward cusp structure at the threshold for excitation of one quantum of the vibrational symmetric deformation mode nu(3), indicating that this mode is active in the primary attachment process. With reference to our thermal attachment rate coefficient k(T = 300 K) = 3.9(2) x 10(-9) cm(3) s(-1), a new highly resolved absolute attachment cross section for T-G = 300 K was determined. This cross section is extended to higher energies by measurements, carried out with a pulsed electron beam apparatus which also provided new data for the distinctly weaker fragment anions HCl2- and CCl2-. The resulting total absolute cross section for anion formation is used to calculate the dependence of the attachment rate coefficient k(T-e;T-G) on electron temperature T-e over the range 50-15000 K at the fixed gas temperature T-G = 300 K. In addition, we report the dependence of the relative cross section for Cl- formation on gas temperature T-G = 310-435 K). For comparison with the experimental data, R-matrix calculations have been carried out for the dominant anion channel Cl-. The results recover the main experimental observations and predict the dependence of the DEA cross section on the initial vibrational level nu(3) and on the vibrational temperature. Our results are compared with those of previous electron beam and electron swarm experiments.

Two-Photon Inner-Shell Ionization in the Extreme Ultraviolet

We have observed the simultaneous inner-shell absorption of two extreme-ultraviolet photons by a Xe atom in an experiment performed at the short-wavelength free electron laser facility FLASH. Photoelectron spectroscopy permitted us to unambiguously identify a feature resulting from the ionization of a single electron of the 4d subshell of Xe by two photons each of energy (93 +/- similar to 1) eV. The feature's intensity has a quadratic dependence on the pulse energy. The results are discussed and interpreted within the framework of recent results of ion spectroscopy experiments of Xe obtained at ultrahigh irradiance in the extreme-ultraviolet regime.

Speciation of chloroindate(III) ionic liquids

A range of chloroindate(III) ionic liquid systems was prepared by mixing of 1-alkyl-3-methylimidazolium chloride with indium(III) chloride in various ratios, expressed as the mol fraction of indium(III) chloride, chi(InCl3). For chi(InCl3) 0.50, the products were biphasic (suspensions of a solid in an ionic liquid). Speciation of these chloroindate(III) systems was carried out using a wide range of techniques: differential scanning calorimetry (DSC), polarised optical microscopy (POM), liquid-state and solid-state In-115 NMR spectroscopy, X-ray photoelectron spectroscopy (XPS) and extended X-ray absorption fine structure (EXAFS). Ionic liquids prepared using an excess of the organic chloride (chi(InCl3) 0.5) contained indium(III) chloride powder suspended in a neutral tetrachloroindate ionic liquid.

Electron detachment from negative ions in a short laser pulse

We present an efficient and accurate method to study electron detachment from negative ions by a few-cycle linearly polarized laser pulse. The adiabatic saddle-point method of Gribakin and Kuchiev [Phys. Rev. A 55, 3760 (1997)] is adapted to calculate the transition amplitude for a short laser pulse. Its application to a pulse with N optical cycles produces 2(N + 1) saddle points in complex time, which form a characteristic "smile." Numerical calculations are performed for H(-) in a 5-cycle pulse with frequency 0.0043 a.u. and intensities of 10(10), 5 x 10(10), and 10(11) W/cm(2), and for various carrier-envelope phases. We determine the spectrum of the photoelectrons as a function of both energy and emission angle, as well as the angle-integrated energy spectra and total detachment probabilities. Our calculations show that the dominant contribution to the transition amplitude is given by 5-6 central saddle points, which correspond to the strongest part of the pulse. We examine the dependence of the photoelectron angular distributions on the carrier-envelope phase and show that measuring such distributions can provide a way of determining this phase.

Low-Energy Electron Attachment to the Dichlorodifluoromethane (CCl2F2) Molecule

Results from a joint experimental study of electron attachment to dichlorodifluoromethane (CCl2F2) molecules in the gas phase are reported. In a high resolution electron beam experiment involving two versions of the laser photoelectron attachment method, the relative cross section for formation of the dominant anion Cl- wits measured over the energy range 0.001-1.8 eV at the gas temperature T-G = 300 K. It exhibits cusp structure at thresholds for vibrational excitation of the v(3)(a(1)) mode due to interaction with the attachment channels. With reference to the thermal attachment rate coefficient k(T-e;T-G = 300 K) = 2.2(8) x 10(-9) cm(-3) s(-1) (fitted average from several data), a new highly resolved absolute attachment cross section for TG = 300 K was determined. Partial cross sections for formation of the anions Cl-, Cl-2(-), F-, ClF-, and CCl2F- were measured over the range 0-12 eV, using three different electron beam experiments of medium energy resolution. The dependence of the attachment rate coefficient k(T-e;T-G = 300 K) on electron temperature T-e wits calculated over the range 50-15 000 K, based on a newly constructed total cross section for anion formation at T-G = 300 K. R-matrix Calculations for Cl- production have been carried out for comparison with the experimental data. The R-matrix results are in line with the main experimental observations and predict the dependence of the DEA cross section on the initial vibrational level v(3) and on the vibrational temperature. Furthermore, the cross section for I Vibrational excitation of the v(3) mode hits been computed.

Pretreatment Effect on Pt/CeO2 Catalyst in the Selective Hydrodechlorination of Trichloroethylene

Pt-ceria catalysts present different surface chemistries depending on the preparation method and the pretreatment. The catalytic behavior of Pt/CeO2 catalysts in the hydrodechlorination of trichloroethylene (TCE) to ethylene was examined as a function of the pretreatment conditions and the noble metal precursor salts. Using FTIR and X-ray photoelectron spectroscopy, significant differences were observed in the surface properties of Pt/CeO2 prepared from the H2PtCl6 precursor after different pretreatment procedures (i.e.. reduction or oxidation-reduction). These surface changes are related to chloride residues from the synthesis. Strong changes were observed in the selectivity of the catalysts to ethylene depending on the pretreatment conditions. The 0.5%Pt/CeO2 catalyst showed a 13% selectivity toward ethylene after reduction, whereas alter oxidation, followed by reduction, the selectivity increased up to 85% at the same conversion level. This effect was only observed when a chloride-containing precursor was used in the preparation. In this way, it is demonstrated that the use of a Cl-containing Pt precursor and an air treatment prior to reduction strongly improves the ethylene selectivity of Pt-CeO2 dechlorination catalysts. This can be explained by formation or a CeOCl phase during the synthesis that decomposes upon air tempering, producing oxygen vacancies on the ceria support. We propose that these oxygen vacancies are active for cleaving off Cl from the TCE. Pt then supplies II to clean-off Cl as HCl. Reaction of TCE on Pt produces rather ethane, so Pt may be partly Cl-poisoned for the hydrodechlorination reaction but not for II, dissociation or CO adsorption.

Structural and magnetic properties of sol-gel Co2xNi0.5-xZn0.5-xFe2O4 thin films

Nanocrystalline Co2xNi0.5-xZn0.5-xFe2O4 (x = 0-0.5) thin films have been synthesized with various grain sizes by a sol-gel method on polycrystalline silicon substrates. The morphology as well as magnetic and microwave absorption properties of the films calcined at 1073 K were studied using X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and vibrating sample magnetometry. All films were uniform with out microcracks . The Co content in the Co-Ni-Zn films resulted in a grain size ranging from 15 to 32 nm while it ranged from 33 to 49 nm in the corresponding powders. Saturation and remnant magnetization increased with increase in grain size, while coercivity demonstrated a drop due to multidomain behavior of crystallites for a given value of x. Saturation magnetization increased and remnant magnetization had a maximum as a function of grain size in dependent of x. In turn, coercivity increased with x independent of grain size. Complex permittivity of the Co-Ni-Zn ferrite films was measured in the frequency range 2-15 GHz. The highest hysteretic heating rate in the temperature range 315-355 K was observed in CoFe2O4. The maximum absorption band shifted from 13 to 11GHz as cobalt content increased from x = 0.1 to 0.2.

Structural investigations and magnetic properties of sol-gel Ni0.5Zn0.5Fe2O4 thin films for microwave heating

Nanocrystalline Ni0.5Zn0.5Fe2O4 thin films have been synthesized with various grain sizes by a sol-gel method on polycrystalline silicon substrates. The morphology, magnetic, and microwave absorption properties of the films calcined in the 673-1073 K range were studied with x-ray diffraction, scanning electron microscopy, x-ray photoelectron spectroscopy, atomic force microscopy, vibrating sample magnetometry, and evanescent microwave microscopy. All films were uniform without microcracks. Increasing the calcination temperature from 873 to 1073 K and time from 1 to 3 h resulted in an increase of the grain size from 12 to 27 nm. The saturation and remnant magnetization increased with increasing the grain size, while the coercivity demonstrated a maximum near a critical grain size of 21 nm due to the transition from monodomain to multidomain behavior. The complex permittivity of the Ni-Zn ferrite films was measured in the frequency range of 2-15 GHz. The heating behavior was studied in a multimode microwave cavity at 2.4 GHz. The highest microwave heating rate in the temperature range of 315-355 K was observed in the film close to the critical grain size.

Facile in situ synthesis of nanofluids based on ionic liquids and copper oxide clusters and nanoparticles

Two stable nanofluids comprising of mixed valent copper(_I,_II) oxide clusters (<1 nm) suspended in 1-butyl-3-methylimidazolium acetate, [C(₄)mim][OAc], and copper(_II) oxide nanoparticles (<50 nm) suspended in trioctyl(dodecyl) phosphonium acetate, [P-₈₈₈₁₂][OAc], were synthesised in a facile one-pot reaction from solutions of copper(_II) acetate hydrate in the corresponding ionic liquids. Formation of the nanostructures was studied using ¹³C NMR spectroscopy and differential scanning calorimetry (DSC). From a solution of Cu(OAc)₂ in 1-ethyl-3-methylimidazolium acetate, [C₂mim][OAc], crystals were obtained that revealed the structure of [C₂mim][Cu₃(OAc)₅(OH)₂(H₂O)]center dot H₂O, indicating the formation of copper hydroxo-clusters in the course of the reaction. Synthesised nanostructures were studied using transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Physical properties of the prepared IL-nanofluids were examined using IR and UV-VIS spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and densitometry.