Simple analyzer for continuous monitoring of sulfur dioxide in gas streams

The construction, optimization and use of simple and inexpensive gas analyzer for real time measurement of sulfur dioxide in gas streams are described. The analyzer consisted of three main components (i) a custom fabricated hollow fiber membrane (HFM) gas contactor, (ii) carrier solution which absorbs SO₂ molecules from the gas stream in the HFM gas contactor and (iii) a flow-through detector placed downstream which continuously measures the changes occurred to the carrier solution upon absorption of SO₂ molecules. The significant acidic properties of the produced sulfurous acid suggested pH and conductivity detectors to monitor the decrease in pH or the increase in the conductivity which constituted the basis for quantification of SO₂ in the gas line. Aqueous potassium oxalate (10^? 1 mol/L) and hydrogen peroxide (10^? 3 mol/L) were used as carrier solutions in combination with pH and conductivity detectors, respectively. The analyzer equipped with pH detector provided linear potentiometric response to SO₂ concentration up to 1000 ppm with Nernstian slop of 61 mV/log[SO₂]. Excellent SO₂ recoveries (97–108%) were obtained in the presence of several folds of potentially interfering acidic gases, i.e., CO₂ and H₂S. The conductivity detector provided linear response up to 2500 ppm. Under optimized conditions, both detectors offered several favorable performance characteristics such as (i) fast response and recovery times, (ii) excellent signal stability and reproducibility (RSD = 0.5%), (iii) intrinsic high selectivity to most common neutral gases, e.g., CH₄, N₂, O₂, CO, etc. The suggested analyzer was applied successfully in monitoring the removal of SO₂ from SO₂–N₂ gas mixtures with hollow fiber membrane contactor using distilled water or aqueous sodium hydroxide as stripping solvents.     

Electrochemical performance of a novel CoTETA/C catalyst for the oxygen reduction reaction

In this communication, we report a novel CoTETA/C catalyst for the oxygen reduction reaction (ORR) which was prepared from a carbon-supported cobalt triethylenetetramine chelate, followed by heat treatment in an inert atmosphere. Electrochemical performances were measured using rotating disk electrode (RDE) technique and a PEM fuel cell test station. For a H₂–O₂ fuel cell system, the maximum output power density reached 162 mW cm^?2 at 25 °C with non-humidified reaction gases. We found a nanometallic face-centered cubic (fcc) α-Co phase embedded in the graphitic carbon after pyrolysis, based on X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) measurements. These results indicated that CoTETA/C is a promising catalyst for the ORR.     

In situ X-ray absorption and diffraction studies of carbon coated LiFe1/4Mn1/4Co1/4Ni1/4PO4 cathode during first charge

Synchrotron based in situ X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) techniques are used to study electronic and crystal structure changes of the carbon coated LiFe_1/4Mn_1/4Co_1/4Ni_1/4PO₄ (LiFe_1/4Mn_1/4Co_1/4Ni_1/4PO₄/C) cathode material for Li-ion batteries during the first charge. In situ Fe, Mn, Co and Ni K-edge XAS results revealed that the three voltage plateaus at ～3.6, 4.2 and 4.7 V vs. Li/Li⁺ are attributed to the redox reactions of Fe²⁺/Fe³⁺, Mn²⁺/Mn³⁺ and Co²⁺/Co³⁺, respectively, while the apparent capacities above 4.9 V is not originated from the Ni²⁺/Ni³⁺ redox, but very likely from the electrolyte decomposition. Interesting phase transition behaviors of LiFe_1/4Mn_1/4Co_1/4Ni_1/4PO₄/C were observed with the formation of an intermediate phase and the solid solution regions. Combined in situ XAS and XRD techniques indicate fast electronic structural changes and slow bulk crystal structural changes.     

Na4Co2.4Mn0.3Ni0.3(PO4)2P2O7: High potential and high capacity electrode material for sodium-ion batteries

Na₄Co_2.4Mn_0.3Ni_0.3(PO₄)₂P₂O₇ has been evaluated as a positive electrode for sodium-ion batteries. The novel material has two redox couples around 4.2 V and 4.6 V and can deliver the high capacity of ca. 103 mAh g^− 1 at the high current density of 850 mA g^− 1 (5 C). X-ray absorption spectroscopy (XAS) results show that the redox reactions of Co, Mn and Ni ions proceed simultaneously in the charge process and it is indicated the novel material provide high mixed potential by the redox reactions of Co, Mn and Ni ions. These findings suggest that the derivatives of Na₄Co₃(PO₄)₂P₂O₇ should be employed as high potential and high capacity electrode materials.     

Demetallation of methemoglobin in cellulose nanofibril–TiO2 nanoparticle composite membrane electrodes

Porous composite films containing cellulose nanofibrils (from sisal) and TiO₂ nanoparticles (ca. 6 nm diameter) are obtained in a layer-by-layer assembly process. Each layer consists of ca. 0.18 μg cellulose nanofibrils and ca. 0.72 μg TiO₂ (determined by QCMB) and adds a thickness of ca. 16 nm (by AFM) to the uniform deposit. The TiO₂ nanophase is creating conducting pathways for electrons in a relatively open cellulose structure (ca. 82% open pores) potentially suitable for the immobilization of large redox proteins such as methemoglobin.Methemoglobin is shown to readily adsorb into the cellulose–TiO₂ film. However, electrochemical responses for the immobilized methemoglobin in aqueous 0.1 M phosphate buffer at pH 5.5 suggest that facile demetallation occurs. Experiments with Fe³⁺ in the absence of protein result in voltammetric responses indistinguishable from those observed for immobilized methemoglobin. In the presence of ethylenediamine tetraacetic acid (EDTA) the voltammetric signals for the Fe³⁺ immediately disappear. Complementary experiments conducted in 0.1 M acetate buffer at pH 5.5 demonstrate that methemoglobin can indeed be immobilized in electrochemically active form and without demetallation loss of the voltammetric signal in the presence of EDTA. Demetallation appears to occur (i) in the presence of phosphate, (ii) at pH 5.5, (iii) and in the presence of a charged surface.     

Li(4−x)/3Ti(5−2x)/3CrxO4 (0 ≤ x ≤ 0.9) spinels: New negatives for lithium batteries

Members of the spinel solid solution between Li_4/3Ti_5/3O₄ and LiCrTiO₄, i.e., Li_(4−x)/3Ti_(5−2x)/3Cr_xO₄ (0 ≤ x ≤ 0.9), have been investigated as possible negative electrodes for future lithium-ion batteries. Electrochemical behaviour have been studied over the potential range 1–3.5 V vs Li⁺/Li. Results are promising with anodic capacities between 129 and 163 mA h/g with a flat operating voltage at about 1.5 V, which is attributed to the pair Ti⁴⁺/Ti³⁺. The inclusion of Cr³⁺ in the spinel structure enhances the specific capacity. In-situ X-ray diffraction experiments confirm that the reaction proceeds in a topotactic manner.     

Synthesis and properties of the compound: LiNi3/5Cu2/5VO4

The LiNi_3/5Cu_2/5VO₄ is synthesized by solution-based chemical method and its formation has been checked by X-ray diffraction (XRD) study. XRD study shows a tetragonal unit cell structure with lattice parameters of a = 11.6475 (18) Å, c = 2.4855 (18) Å and c/a = 0.2134 Å. Electrical properties are verified using complex impedance spectroscopy (CIS) technique. Complex impedance analysis reveals following points: (i) the bulk contribution to electrical properties up to 200 °C, (ii) the bulk and grain boundary contribution at T ≥ 225 °C, (iii) the presence of temperature dependent electrical relaxation phenomena in the material. D.c. conductivity study indicates that electrical conduction in the material is a thermally activated process.     

A Miniature glucose/O2 biofuel cell with single-walled carbon nanotubes-modified carbon fiber microelectrodes as the substrate

This study demonstrates a new kind of miniature glucose/O₂ biofuel cells (BFCs) based on carbon fiber microelectrodes (CFMEs) modified with single-walled carbon nanotubes (SWNTs). SWNTs are used as a support both for stably confining the electrocatalyst (i.e., methylene green, MG) for the oxidation of NADH and the anodic biocatalyst (i.e., NAD⁺-dependent glucose dehydrogenase, GDH) for the oxidation of glucose and for efficiently facilitating direct electrochemistry of the cathodic biocatalyst (i.e., laccase) for the O₂ reduction. The prepared micro-sized GDH-based bioanode and laccase-based biocathode exhibit good bioelectrocatalytic activity toward the oxidation of glucose and the reduction of oxygen, respectively. In 0.10 M phosphate buffer containing 10 mM NAD⁺ and 45 mM glucose under ambient air, the power density of the assembled miniature compartment-less glucose/O₂ BFC reaches 58 μW cm⁻² at 0.40 V. The stability of the miniature glucose/O₂ BFC is also evaluated.     

A novel method for preparing PEMFC electrodes by the ultrasonic and sonoelectrochemical techniques

Novel ultrasonic and sonoelectrochemical methods for preparing Proton Exchange Membrane Fuel Cell (PEMFC) electrodes are described. Platinum loaded on Nafion-bonded carbon anodes in Membrane Electrode Assemblies (MEAs) were prepared in K₂PtCl₄ aqueous solutions by galvanostatic pulse electrodeposition in the absence and presence of power ultrasound (20 kHz). It was found that PEMFC electrodes prepared sonoelectrochemically showed better performance compared to those prepared by (i) galvanostatic pulse method only (i.e. silent conditions) and (ii) conventional method. Maximum power densities of 98.5 mW cm^?2 were found for anodes prepared sonoelectrochemically compared with 91.5 mW cm^?2 (by galvanostatic pulse method alone) and 86 mW cm^?2 (by conventional method).     

Synthesis and characterization of hierarchically structured mesoporous MnO2 and Mn2O3

Hierarchically structured mesoporous MnO₂ with high surface area was prepared by a facile precursor route. Well-defined morphological manganese oxalate, synthesized by adding l-lysine via a hydrothermal method, was used as precursor. Mesoporous amorphous MnO₂ with high Brunauer–Emmett–Teller (BET) surface area (340 m²/g) and mesoporous Mn₂O₃ composed of nano-crystals (BET surface area 188 m²/g) were obtained by selective calcination of the oxalate precursor at 330 °C and 400 °C, respectively. Thermogravimetric and differential thermal analyses (TG–DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂-sorption analysis and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure and property of products. Cyclic voltammetry (CV) and charge–discharge measurements were used to preliminarily study the electrochemical performance of the products. The range of pH value (about 5.0–7.0) in the synthesis process is apt to prepare the hierarchical structured manganese dioxide. Other types of amino acids were also employed as the crystallization modifiers and different morphologies of manganese dioxides were obtained.     

Suppression of dendritic lithium formation by using concentrated electrolyte solutions

This study examined the electrochemical deposition and dissolution of lithium on nickel electrodes in a propylene carbonate (PC) electrolyte containing different LiN(SO₂C₂F₅)₂ concentrations. The electrolyte concentration was found to have a significant effect on the reactions occurring at the electrode. The poor cycleability of the electrodes in the low-concentration solutions was improved considerably by increasing the electrolyte concentration. Transmission electron microscopy (TEM) revealed that a high-concentration solution produces a thinner solid electrolyte interphase (SEI) on the electrodeposited lithium than a low-concentration solution, e.g., ∼35 nm in 1.28 mol kg⁻¹ vs. ∼20 nm in 3.27 mol kg⁻¹ solutions. Raman spectroscopy showed that the solvation number of lithium ions differed according to the electrolyte concentration. This suggests that the structure of solvated lithium ions is an important factor in suppressing dendritic lithium formation.     

Novel concept of pseudocapacitor using stabilized lithium metal powder and non-lithiated metal oxide electrodes in organic electrolyte

A concept of using two non-prelithiated metal oxides (e.g., MnO₂, V₂O₅, and FeO_x) in both positive and negative electrodes in organic Li-ion electrolytes has been proposed and tested to improve the energy density of pseudocapacitors. To take the advantages of this concept, additional lithium source is essential to provide lithium ions during the charge–discharge cycles. The stabilized lithium metal powder (SLMP^?) developed by FMC Corp., provides such an essential Li⁺ source. Here we report the first result of the symmetric pseudocapacitor using two non-prelithiated metal oxide (i.e., manganese oxide/carbon nanotube (MnO₂/CNT)) electrodes, with added SLMP in one of them. The capacitor using the SLMP added MnO₂/CNT (positive) and pure MnO₂/CNT (negative) electrode in 1.2 M LiPF₆-EC:EMC electrolyte shows supercapacitive behaviors in 3.0 V voltage range. The addition of SLMP opens new opportunities of using the non-lithiated metal oxide electrodes in pseudocapacitors and hybrid electrochemical capacitors (ECs), which has not been possible before.     

Non-metallic gold nanoclusters for oxygen activation and aerobic oxidation

In this review, oxygen activation and their aerobic oxidation over the Au nanoclusters are presented. The size-specificity, ligand engineering, and doping effects and the proposed reactions’ mechanism and the structure-activity relationships at the atomic level are also discussed.     

Functionalized N-heterocyclic carbene iridium complexes: Synthesis,structure and addition polymerization of norbornene

Picolyl, pyridine, and methyl functionalized N-heterocyclic carbene iridium complexes [Cp¹Ir(C^N)Cl]Cl (4, C^N = 3-Methyl-1-picolyimidazol-2-ylidene), [Cp¹Ir(C^N)Cl][Cp¹IrCl₃] (5), [Cp¹Ir(C-N)Cl]Cl (6, C-N = 3-Methyl-1-pyridylimidazol-2-ylidene) and [Cp¹Ir(L)Cl₂] (7, L = 1,3-dimethylimidazol-2-ylidene) have been synthesized by transmetallation from Ag(I) carbene species, and characterized by ¹H NMR, ¹³C NMR spectra and elemental analyses. The molecular structures of 5–7 have been confirmed by X-ray single-crystal analyses. The iridium carbene complexes 4 and 6 show moderate catalytic activities (3.03 × 10⁵ g PNB (mol Ir)^?1 h^?1 and 1.70 × 10⁶ g PNB (mol Ir)^?1 h^?1) for the addition polymerization of norbornene in the presence of methylaluminoxane (MAO) as co-catalyst. The produced polynorbornene have been characterized by IR, ¹H NMR and ¹³C NMR spectra, showing it follows the vinyl-addition-type of polymerization.     

The thioantimonate anion [Sb4S8]4− acting as a tetradentate ligand: Solvothermal synthesis,crystal structure and properties of {[In(C6H14N2)2]2Sb4S8}Cl2 exhibiting unusual uniaxial negative and biaxial positive thermal expansion

The new compound {[In(C₆H₁₄N₂)₂]₂Sb₄S₈}Cl₂ was prepared under solvothermal conditions reacting InCl₃, Sb and S using 1,2-trans-diaminocyclohexane as solvent and structure directing molecule. The compound crystallizes in the monoclinic space group C2/c with a = 29.0259(12), b = 6.7896(2), c = 24.2023(12) Å, β = 99.524(4)°, V = 4703.9(3) ų. The central structural motif is the thioantimonate(III) anion [Sb₄S₈]^4? acting as a tetradentate ligand thus joining two symmetry related In³⁺ centered complexes. This binding mode was never observed before for the [Sb₄S₈]^4? anion. The optical band gap was determined as 2.03 eV in agreement with the red color of the compound. The thermal decomposition was monitored with in-situ X-ray diffraction experiments. After the emission of the amine molecules an amorphous intermediate is formed followed by the crystallization of InSbS₃ which is stable up to about 590 °C. On further heating, InSbS₃ is destroyed and reflections of γ-In₂S₃ appear being contaminated with some elemental Sb. Temperature dependent in-situ X-ray powder diffractometry performed between 30 and 220 °C reveals an unusual reversible negative and positive thermal expansion. The decrease of the a-axis in the temperature range is about 0.74 Å and the increase of the c-axis ca. 0.54 Å. Interestingly, the b-axis exhibits also a thermal expansion, i.e., a biaxial positive and an uniaxial negative thermal expansion coexist which is very unusual. The relative negative expansion coefficients for the a-axis of ?194 × 10^?6K^?1 (30–120 °C) and ?82 × 10^?6K^?1 (120–220 °C) are in the region of so-called colossal thermal expansion.     

Structural and electrochemical investigation of Li2MgSnO4 anode for lithium batteries

Hexagonal Li₂MgSnO₄ compound was synthesized at 800 °C using Urea Assisted Combustion (UAC) method and the same has been exploited as an anode material for lithium battery applications. Structural investigations through X-ray diffraction, Fourier Transform Infra Red spectroscopy and ⁷Li NMR (Nuclear Magnetic Resonance spectroscopy) studies demonstrated the existence of hexagonal crystallite structure with a = 6.10 and c = 9.75. An average crystallite size of ∼400 nm has been calculated from PXRD pattern, which was further evidenced by SEM images. An initial discharge capacity of ∼794 mA h/g has been delivered by Li₂MgSnO₄ anode with an excellent capacity retention (85%) and an enhanced coulombic efficiency (97–99%). Further, the Li₂MgSnO₄ anode material has exhibited a steady state reversible capacity of ∼590 mA h/g even after 30 cycles, thus qualifying the same for use in futuristic lithium battery applications.     

The precise measurement of the (vapour + liquid) equilibrium properties for (CO2 + isobutane) binary mixtures

Recently, it has been suggested that natural working fluids, such as CO₂, hydrocarbons, and their mixtures, could provide a long-term alternative to fluorocarbon refrigerants. (Vapour + liquid) equilibrium (VLE) data for these fluids are essential for the development of equations of state, and for industrial process such as separation and refinement. However, there are large inconsistencies among the available literature data for (CO₂ + isobutane) binary mixtures, and therefore provision of reliable and new measurements with expanded uncertainties is required. In this study, we determined precise VLE data using a new re-circulating type apparatus, which was mainly designed by Akico Co., Japan. An equilibrium cell with an inner volume of about 380 cm³ and two optical windows was used to observe the phase behaviour. The cell had re-circulating loops and expansion loops that were immersed in a thermostatted liquid bath and air bath, respectively. After establishment of a steady state in these loops, the compositions of the samples were measured by a gas chromatograph (GL Science, GC-3200). The VLE data were measured for CO₂/propane and CO₂/isobutane binary mixtures within the temperature range from 300 K to 330 K and at pressures up to 7 MPa. These data were compared with the available literature data and with values predicted by thermodynamic property models.     

Intramolecularly donor-stabilized silenes: Part 6. The synthesis of 1-[2,6-bis(dimethylaminomethyl)phenyl]silenes and their reaction with aromatic aldehydes

The intramolecularly donor-stabilized silenes ArR¹SiC(SiMe₃)₂ (3a–d) (3a: R¹ = Me; 3b: R¹ = t-Bu; 3c: R¹ = Ph; 3d: R¹ = SiMe₃; Ar = 2,6-(Me₂NCH₂)₂C₆H₃) were prepared by treatment of the (dichloromethyl)oligosilanes (Me₃Si)₂R¹Si–CHCl₂ (1a–d), with 2,6-bis(dimethylaminomethyl)phenyllithium (molar ratio 1:2). For 3c and 3d, X-ray structural analyses were performed indicating that only one dimethylamino group of the tridentate ligand is coordinated to the electrophilic silene silicon atoms, i.e., the central silicon atoms are tetracoordinated. The N → Si donation leads to pyramidalization at the silene silicon atoms; the configuration at the silene carbon atoms is planar. For a chemical characterization 3a and 3c were treated with water to give the silanols ArR¹Si(OH)–CH(SiMe₃)₂ (5a,c). Studies of the reactions of 3a and 3c with benzaldehyde, 4-chlorobenzaldehyde or 4-methoxybenzaldehyde, respectively, revealed an unexpected reaction path leading to the substituted 2-oxa-1-sila-1,2,3,4-tetrahydronaphthalenes 12a, 12c, 13 and 14. Both 12a and 12c were structurally characterized by X-ray analyses. The formation of these six-membered cyclic compounds, which is discussed in detail, gives support to a dipolar mechanism for the general reaction of silenes with carbonyl derivatives.     

Short chain lead (II) alkanoates as ionic liquids and glass formers: A d.s.c., X-ray diffraction and FTIR spectroscopy study

Three members of the lead (II) n-alkanoates (from etanoate to n-butanoate) have been synthesized, purified and studied by d.s.c., X-ray diffraction, and FTIR spectroscopy. Lead (II) acetate, propanoate, and butanoate present only a melting transition at T = (452.6, 398.2, and 346.5) K, with Δ_fH = (16.0, 13.1, and 15.6) kJ · mol⁻¹, and Δ_fS = (35.3, 32.8, and 45.1) J · mol⁻¹ · K⁻¹, respectively. These temperature data correct to a great extent the historical values reported in the literature. These three members readily quench into a glass state. Their corresponding T_g values are (314.4, 289.0, and 274.9) K, respectively, measured by d.s.c. at a heating rate of 5 K · min⁻¹.     

Effect of bication (Cu-Cr) substitution on the structure and electrochemical performance of LiMn2O4 spinel cathodes at low and high current rates

This report describes the detailed structural and electrochemical characterization of a series of low content (0.01 to 0.05) Cu-Cr bi-metal doped LiMn₂O₄ cathode material synthesized by sol–gel method. The structural and morphological features were described using XRD, SEM, TEM, EDAX and FTIR techniques. The electron transfer and its feasibility were discussed through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements. The charge–discharge studies were performed to evaluate the capacity fading and rate capability. It was found that the electrochemical performance is very much dependent on the amount of Cu-Cr bi-metal doping and interestingly decreased the capacity fading with high cycleability. The sample with the least amount of dopants (i.e., LiCu_0.01Cr_0.01Mn_1.98O₄) demonstrated much improved capacity, cycleability and high rate capability. The LiCu_0.01Cr_0.01Mn_1.98O₄ cathode exhibited a discharge capacity of 112 mA h g^?1 at very first cycle and retained 93 mA h g^?1 after 100 cycles at a C rate of 0.3. Further, the same material at very high current density (5 C) retained 83% of the initial discharge capacity. The Cu-Cr doping stabilized the spinel structure by suppressing the Jahn-Teller distortion effect and Mn dissolution and the resultant material showed the workability of the cathodes for devices which work at substantially high C-rate of 5C.