Vibrational spectroscopic study of the antimonate mineral bindheimite Pb2Sb2O6(O,OH)

Raman spectroscopy complimented with infrared spectroscopy has been used to characterise the antimonate mineral bindheimite Pb₂Sb₂O₆(O,OH). The mineral is characterised by an intense Raman band at 656 cm⁻¹ assigned to SbO stretching vibrations. Other lower intensity bands at 664, 749 and 814 cm⁻¹ are also assigned to stretching vibrations. This observation suggests the non-equivalence of SbO units in the structure. Low intensity Raman bands at 293, 312 and 328 cm⁻¹ are assigned to the OSbO bending vibrations. Infrared bands at 979, 1008, 1037 and 1058 cm⁻¹ may be assigned to δOH deformation modes of SbOH units. Infrared bands at 1603 and 1640 cm⁻¹ are assigned to water bending vibrations, suggesting that water is involved in the bindheimite structure. Broad infrared bands centred upon 3250 cm⁻¹ supports this concept. Thus the true formula of bindheimite is questioned and probably should be written as Pb₂Sb₂O₆(O,OH,H₂O).     

Vibrational spectroscopic study of the arsenate mineral strashimirite Cu8(AsO4)4(OH)4·5H2O—Relationship to other basic copper arsenates

The basic copper arsenate mineral strashimirite Cu₈(AsO₄)₄(OH)₄·5H₂O from two different localities has been studied by Raman spectroscopy and complemented by infrared spectroscopy. Two strashimirite mineral samples were obtained from the Czech (sample A) and Slovak (sample B) Republics. Two Raman bands for sample A are identified at 839 and 856 cm⁻¹ and for sample B at 843 and 891 cm⁻¹ are assigned to the ν₁ (AsO₄³⁻) symmetric and the ν₃ (AsO₄³⁻) antisymmetric stretching modes, respectively. The broad band for sample A centred upon 500 cm⁻¹, resolved into component bands at 467, 497, 526 and 554 cm⁻¹ and for sample B at 507 and 560 cm⁻¹ include bands which are attributable to the ν₄ (AsO₄³⁻) bending mode. In the Raman spectra, two bands (sample A) at 337 and 393 cm⁻¹ and at 343 and 374 cm⁻¹ for sample B are attributed to the ν₂ (AsO₄³⁻) bending mode. The Raman spectrum of strashimirite sample A shows three resolved bands at 3450, 3488 and 3585 cm⁻¹. The first two bands are attributed to water stretching vibrations whereas the band at 3585 cm⁻¹ to OH stretching vibrations of the hydroxyl units. Two bands (3497 and 3444 cm⁻¹) are observed in the Raman spectrum of B. A comparison is made of the Raman spectrum of strashimirite with the Raman spectra of other selected basic copper arsenates including olivenite, cornwallite, cornubite and clinoclase.     

Characterization of a 10.3-μm pulsed DFB quantum cascade laser

We have measured the output parameters of a 10.3-μm pulsed distributed-feedback (DFB) quantum cascade (QC) laser manufactured by Alpes Lasers and intended for high-sensitivity detection of ammonia and ethylene. The laser beam was collimated with an AR-coated aspheric ZnSe lens with focal length of 11.6 mm and clear aperture of 16.5 mm. Near- and far-field distributions of the laser emission were recorded with an infrared imaging camera. The fast-and slow-axis laser beam divergences were measured to be 1.2 and 1.4 mrad (FWHM), respectively. The divergence was found to be increasing with injection current. An air-spaced Fabry–Perot interferometer with free spectral range of 0.05 cm⁻¹ was used to measure the frequency tuning rates of the laser. The laser was tuned by either heat sink temperature, injection current or pulse repetition rate with rates of −8 × 10⁻² cm⁻¹ K⁻¹, −7 × 10⁻² cm⁻¹ A⁻¹ and −9 × 10⁻⁴ cm⁻¹ kHz⁻¹, respectively. The laser frequency decreased linearly with a rate of 10⁻² cm⁻¹ ns⁻¹ (300 MHz ns⁻¹) for laser pulses varied from 10 to 50 ns, and the frequency chirp rate was found to decrease for longer laser pulses.     

Energetics of copper diphosphates – Cu2P2O7 and Cu3(P2O6OH)2

Differential scanning calorimetry and high temperature oxide melt solution calorimetry are used to study enthalpy of phase transition and enthalpies of formation of Cu₂P₂O₇ and Cu₃(P₂O₆OH)₂. α-Cu₂P₂O₇ is reversibly transformed to β-Cu₂P₂O₇ at 338–363 K with an enthalpy of phase transition of 0.15 ± 0.03 kJ mol⁻¹. Enthalpies of formation from oxides of α-Cu₂P₂O₇ and Cu₃(P₂O₆OH)₂ are −279.0 ± 1.4 kJ mol⁻¹ and −538.8 ± 2.7 kJ mol⁻¹, and their standard enthalpies of formation (enthalpy of formation from elements) are −2096.1 ± 4.3 kJ mol⁻¹ and −4302.7 ± 6.7 kJ mol⁻¹, respectively. The presence of hydrogen in diphosphate groups changes the geometry of Cu(II) and decreases acid–base interaction between oxide components in Cu₃(P₂O₆OH)₂, thus decreasing its thermodynamic stability.     

An unprecedented Cu–Schiff base complex existing as two different trinuclear units with strong antiferromagnetic couplings

A new tetradentate N₂O₂ donor Schiff base ligand [OHC₆H₄CHNCH₂CH₂CH(CH₂CH₃)NCHC₆H₄OH = H₂L ] was obtained by 1:2 condensation of 1,3-diaminopentane with salicylaldehyde and has been used to synthesise an unusual copper(II) complex whose asymmetric unit presents two structurally different almost linear trinuclear units [Cu₃(μ-L)₂(ClO₄)₂] [Cu₃(μ-L)₂(H₂O)(ClO₄)₂] (1). The ligand and the complex were characterised by elemental analysis, FT-IR, ¹H NMR and UV–Vis spectroscopy in addition electrochemical and single crystal X-ray diffraction studies were performed for the complex. The magnetic properties of 1 reveal the presence of strong intra-trimer (J₁ = −202(3) cm⁻¹ and J₂ = −233(3) cm⁻¹) as well as very weak inter-trimer (zJ′ = −0.11(1) cm⁻¹) antiferromagnetic interactions.     

Cathodic electrophoretic deposition of manganese dioxide films

Cathodic electrophoretic deposition (EPD) method has been developed for the deposition of manganese dioxide films. It was shown that phosphate ester (PE) is an effective charging additive, which provides stabilization of manganese dioxide nanoparticles in suspensions. The influence of PE concentration and deposition voltage on the deposition efficiency has been studied. EPD has been utilized for the fabrication of porous nanostructured films with thickness in the range of 0.5–20 μm for application in electrochemical supercapacitors (ES). Cyclic voltammetry and chronopotentiometry data for the films tested in the 0.1 M Na₂SO₄ solutions showed capacitive behavior in the voltage window of 1 V. The highest specific capacitance (SC) of 377 F g⁻¹ was obtained at a scan rate of 2 mV s⁻¹. The SC decreased with increasing film thickness and increasing scan rate in the range of 2–100 mV s⁻¹. The deposition mechanism, kinetics of deposition and charge storage properties of the films are discussed.     

Enhanced tungstate electrochromism via formation of transparent conductive networks

Indium tin oxide (ITO) nanopowder was added to a polymer film containing WO₃ · H₂O particles to enhance electron conductivity and complimentary Li ion kinetics in an electrochromic device. Film conductivity increased dramatically with ITO content, suggesting the formation of conductive ITO networks in the film. The improved electron conductivity leads to a substantial increase of the effective Li⁺ ion diffusion coefficient in the composite film, from 10⁻¹¹ to 10⁻⁹ cm²/s. Electrochromic contrast studies revealed that the presence of the ITO networks leads to enhanced blue/green color contrast.     

Molecular fine structure and transition dipole moment of NO2 using an external cavity quantum cascade laser

Rotational vibrational fine structure and transition dipole moment of NO₂ is measured using Doppler free saturation spectroscopy with an external grating cavity quantum cascade laser (QCL). The QCL wavelength is calibrated using a 310 cm long internally coupled Fabry–Perot interferometer. We obtain a frequency splitting of 139.68 ± 0.06 MHz (0.0047 cm⁻¹) between the spin doublets (17) of 000 → 001 transition of NO₂. The resolution of the QCL based saturation spectrometer is limited by the QCL linewidth of 3.99 MHz ( 0.00013 cm⁻¹) deduced from the half width of the Lamb dips. The Lamb dip spectroscopy is utilized to obtain a vibrational dipole moment of 0.37 Debye for the (17) transitions.     

Amperometric glucose biosensor based on a gold nanorods/cellulose acetate composite film as immobilization matrix

We report on the utilization of gold nanorods to create a highly responsive glucose biosensor. The feasibility of an amperometric glucose biosensor based on immobilization of glucose oxidase (GOx) in gold nanorod is investigated. GOx is simply mixed with gold nanorods and cross-linked with a cellulose acetate (CA) medium by glutaraldehyde. The adsorption of GOx on the gold nanorods is confirmed by X-ray photoelectron spectroscopy (XPS) measurements. Circular dichroism (CD) and UV-spectrum results show that the activity of GOx was preserved after conjugating with gold nanorods. The current response of modified electrode is 10 times higher than that of without gold nanorods. Under optimal conditions, the biosensor shows high sensitivity (8.4 μA cm⁻² mM⁻¹), low detection limit (2 × 10⁻⁵ M), good storage stability and high affinity to glucose (). A linear calibration plot is obtained in the wide concentration range from 3 × 10⁻⁵ to 2.2 × 10⁻³ M.     

Fourier transform infrared study of mercury interaction with carboxyl groups in humic acids

An interaction between humic acid, an organic part of soil and mercury was studied by Fourier transform infrared spectroscopy (FTIR) and by ICP-AES analysis under given pH and concentration conditions. First the spectroscopic model was validated on the interaction of simple molecules representing the structural components of humic acid such as benzoic acid, catechol and salicylic acid with mercury. The interaction of carboxylic parts of humic acid with mercury is very interesting and easily characterised by infrared spectroscopy, an ideal mean for molecular study. Under the salt form (commercial humic acid Fluka TM: FHA), humic acid reacts with mercury in a different way from its acid form (FHA purified noted PFHA) and the Leonardite (LHA). Because of the straightforward exchange between Na⁺, Ca²⁺ and Hg²⁺, fixation of the latter is much more important with the salt form (FHA). However, this reaction is reduced under the acid form (PFHA, LHA) because the exchange with protons is difficult. The effect of this exchange was studied by FTIR showing the intensity decrease of ν_CO (COOH), the carboxylic functional group band of the acid, and the shifting of ν_as (COO⁻), the carboxylate functional group band under given pH and mercury conditions. For the FHA salt form, the characteristic band ν_CO (COOH) represented by a shoulder did not evolute, whereas the corresponding band to ν_as (COO⁻) strongly shifted (40 cm⁻¹) for a maximum Hg²⁺ concentration (1 g l⁻¹). On the other hand, for the acid form (PFHA, LHA), the intense band of ν_CO (COOH) disappeared proportionally to the increase of Hg²⁺concentration and the ν_as (COO⁻) band moved for about 20 cm⁻¹. The same results were reached with pH variations. Our results were confirmed by ICP-AES mercury analysis. This study shows that humic acids react differently according to their chemical and structural state.     

High-accuracy determination of iron in seawater by isotope dilution multiple collector inductively coupled plasma mass spectrometry (ID-MC-ICP-MS) using nitrilotriacetic acid chelating resin for pre-concentration and matrix separation

In the present paper we describe a robust and simple method to measure dissolved iron (DFe) concentrations in seawater down to <0.1 nmol L⁻¹ level, by isotope dilution multiple collector inductively coupled plasma mass spectrometry (ID-MC-ICP-MS) using a ⁵⁴Fe spike and measuring the ⁵⁷Fe/⁵⁴Fe ratio. The method provides for a pre-concentration step (100:1) by micro-columns filled with the resin NTA Superflow of 50 mL seawater samples acidified to pH 1.9. NTA Superflow is demonstrated to quantitatively extract Fe from acidified seawater samples at this pH. Blanks are kept low (grand mean 0.045 ± 0.020 nmol L⁻¹, n = 21, 3× S.D. limit of detection per session 0.020–0.069 nmol L⁻¹ range), as no buffer is required to adjust the sample pH for optimal extraction, and no other reagents are needed than ultrapure nitric acid, 12 mM H₂O₂, and acidified (pH 1.9) ultra-high purity (UHP) water. We measured SAFe (sampling and analysis of Fe) reference seawater samples Surface-1 (0.097 ± 0.043 nmol L⁻¹) and Deep-2 (0.91 ± 0.17 nmol L⁻¹) and obtained results that were in excellent agreement with their DFe consensus values: 0.118 ± 0.028 nmol L⁻¹ (n = 7) for Surface-1 and 0.932 ± 0.059 nmol L⁻¹ (n = 9) for Deep-2. We also present a vertical DFe profile from the western Weddell Sea collected during the Ice Station Polarstern (ISPOL) ice drift experiment (ANT XXII-2, RV Polarstern) in November 2004–January 2005. The profile shows near-surface DFe concentrations of 0.6 nmol L⁻¹ and bottom water enrichment up to 23 nmol L⁻¹ DFe.     

Dual electrochemical microsensor for simultaneous measurements of nitric oxide and oxygen: Fabrication and characterization

A planar-type amperometric dual microsensor was developed for the simultaneous measurement of the nitric oxide (NO) and oxygen (O₂) concentrations. The sensor (overall diameter = 500 μm) consisted of a dual working electrode (WE) containing two platinized platinum microdisks (25 μm diameter, WE1, WE2, distance between two disks > 330 μm) and a Ag/AgCl wire reference electrode covered with an expanded poly(tetrafluoroethylene) gas-permeable membrane. The differentiation and concurrent measurements of NO and O₂ were obtained successfully using two sensing WEs with different applied potentials (+0.75 V for WE1 and −0.4 V for WE2). Cross-talk between WE1 and WE2 was eliminated with an optimized internal solution composition. Linear dynamic range, selectivity, sensitivity, detection limit (<5 nM for NO; <500 nM for O₂), and stability (>50 h) were evaluated.     

Solvent effect on the blue shifted weakly H-bound F3 CH…FCD3 complex

Solvent effect on the ν^c frequency of CH stretching vibration of the blue shifted F₃CH…FCD₃ complex has been studied in liquefied N₂, CO, Ar, Kr and Xe. In the case of Xe, the spectroscopic measurements have also been extended to the solid state. It was found that the ν^c position of the complex in the solutions studied lowers with respect to the value in the gas phase. In liquid Xe, characterized by the largest permittivity, this effect reaches its maximum value of −14.5 cm⁻¹. The ν^c frequency begins to grow again just below the freezing point of Xe, where a noticeable (15%) increase of the density of Xe occurs. The experimental results obtained for the liquid phase have been analyzed in the framework of the Onsager-like reaction field model and Polarizable Continuum Model (PCM) implemented into a standard Gaussian 98 Program.     

Simultaneous determination of chloride, nitrate and sulphate in vegetable samples by single-column ion chromatography

A new ion chromatography method is described for the simultaneous determination of Cl⁻, NO₃⁻ and SO₄²⁻, using a selected eluent 1.3-mM sodium gluconate/1.3-mM borax (pH 8.5). The extraction methods of Cl⁻, NO₃⁻, SO₄²⁻ in vegetables are studied. The determination limits of Cl⁻, NO₃⁻, SO₄²⁻ are 0.17 μg/ml, 0.63 μg/ml and 0.81 μg/ml. The linear ranges are 060 μg/ml, 090 μg/ml and 090 μg/ml. The relative S.D. are <2.5%. The mean recoveries of Cl⁻, NO₃⁻, SO₄²⁻ in vegetables range from 97.0 to 104%.     

Characterization of Fumed Alumina/Silica/Titania in the Gas Phase and in Aqueous Suspension

Fumed oxide alumina/silica/titania was studied in comparison with fumed alumina, silica, titania, alumina/silica, and titania/silica by means of XRD, ¹H NMR, IR, optical, dielectric relaxation, and photon correlation spectroscopies, electrophoresis, and quantum chemical methods. The explored Al₂O₃/SiO₂/TiO₂ consists of amorphous alumina (22 wt%), amorphous silica (28 wt%), and crystalline titania (50 wt%, with a blend of anatase (88%) and rutile (12%)) and has a wide assortment of Brønsted and Lewis acid sites, which provide a greater acidity than that of individual fumed alumina, silica, or titania and an acidity close to that of fumed alumina/silica or titania/silica. The changes in the Gibbs free energy (ΔG) of interfacial water in an aqueous suspension of Al₂O₃/SiO₂/TiO₂ are close to the ΔG values of the dispersions of pure rutile but markedly lower than those of alumina, anatase, or rutile covered by alumina and silica. The zeta potential of Al₂O₃/SiO₂/TiO₂ (pH of the isoelectric point (IEP) equals ≈3.3) is akin to that of fumed titania (pH(IEP_TiO2) ≈ 6) at pH > 6, but it significantly differs from the ζ of fumed alumina (pH(IEP_Al2O3) ≈ 9.8) at any pH value as well as those of fumed silica, titania/silica, and alumina/silica at pH < 6. The particle size distribution in the diluted aqueous suspensions of Al₂O₃/SiO₂/TiO₂ studied by means of photon correlation spectroscopy depends relatively slightly on pH in contrast to the titania/silica or alumina/silica dispersions. Theoretical calculations of oxide cluster interaction with water show a high probability of hydrolysis of Al–O–Ti and Si–O–Ti bonds strained at the interface of alumina/titania or silica/titania due to structural differences in the lattices of the corresponding individual oxides. Ab initio calculated chemical shift δ_H values of H atoms in different hydroxyl groups at the oxide clusters and in bound water molecules are in agreement with the ¹H NMR data and show a significant impact of charged particles (H₃O⁺ or OH⁻) on the average δ_H values of water droplets with (H₂O)_n at n between 2 and 48.     

Simulation of equivalent weight dependence of Nafion morphologies and predicted trends regarding water diffusion

Microphase separation within hydrated Nafion^® membranes was simulated using Dissipative Particle Dynamics (DPD). Morphologies were obtained at branching densities corresponding with equivalent weights ranging from 800 to 1400 (g/mole SO₃) and water percentage volume contents ([H₂O]) varying between 10% and 30%. All cases showed pronounced microphase separation involving a hydrophobic Teflon phase and a hydrophilic phase in which water is associated with SO₃ groups that are located near the phase boundaries. Pore morphologies were found to depend strongly on water content and branching density. The average pore radius (R_pore) and the distance between the pores (D_cl-cl) were found to increase with water content obeying the relations R_pore = 1.3 + α[H₂O] (nm), and D_cl-cl = 3.2 + β[H₂O] (nm). The values of the expansion coefficients α and β decrease linearly with branching density with α = 5.3 × 10⁻⁵ × (EW-450) and β = 1.3 × 10⁻⁴ × (EW-450) nm/vol%. For decreasing branching density the pores obtain a more spherical character. The consequence of this on water diffusion is estimated by employing Monte Carlo trajectory calculations in which we assume that water movement is confined within the hydrophilic phase and local water mobility to be equal to that of pure water. The estimated diffusion constants increase linearly with branching density (i.e. linear decrease with equivalent weight). Experimental water diffusion constants obtained from literature for Nafion1100 membrane are in good agreement with our calculations. A counterintuitive picture evolves in which smaller pores lead to enhanced water diffusion.     

Existence of clathrate-like structures in supercooled water: X-ray diffraction evidence

X-ray diffraction study of supercooled water has been performed using an imaging-plate X-ray detector down to −15 °C. The peak at 10.8 Å, which grows with decreasing temperature, in the radial distribution function {D(r) − 4πr²ρ₀} indicates the existence of clathrate-like structures in supercooled water. It is suggested that anomalous properties of water, which become more pronounced at low temperatures, are closely linked to the development of clathrate-like structures in water at low temperatures.     

Infrared diode laser spectroscopy of the ν = 2 band of AlF

A vibrational–rotational spectrum of the ν = 2 transitions of a high-temperature molecule AlF was observed between 1490 and 1586 cm⁻¹ with a diode laser spectrometer. Measurements were made on the ν = 3–1, 4–2, 5–3 and 8–6 bands at a temperature of 900 °C. Measured spectral lines were fitted to effective band constants ν₀, B_ν and D_ν for each band. Present measurements were made with only one Pb-salt laser diode. Physical significance of the effective band constants is discussed.     

Electrochemical kinetics and cycling performance of nano Li[Li0.23Co0.3Mn0.47]O2 cathode material for lithium ion batteries

Li[Li_0.23Co_0.3Mn_0.47]O₂ cathode material was prepared by a sol–gel method. The material had a primary particle size of about 100 nm, covered by a 30 Å of Li₂CO₃ layer. The material showed promising electrochemical performance when cycled up to 3C rate. The electrochemical kinetics of the first charge was much slower than that of the second charge, due to the complex electrochemical process which involved not only Li⁺ diffusion but also release of oxygen. By taking account of this, the material was pre-charged very slowly (C/50) in the first cycle. This led to excellent electrochemical performance in the following cycles. For instance, the 1C-rate capacity increased to 168 mA h g⁻¹ after 50 cycles, comparing with the 145 mA h g⁻¹ obtained without pre-charging.