Characterization of thermally aged AlPO<Subscript>4</Subscript>-coated LiCoO<Subscript>2</Subscript> thin films

The electrochemical properties and stability during storage of pristine and AlPO₄-coated LiCoO₂ thin films were characterized. The wide and smooth surface of the thin film electrode might provide an opportunity for one to observe surface reactions with an electrolyte. The rate capability and cyclic performance of the LiCoO₂ thin film were enhanced by AlPO₄ surface coating. Based on secondary ion mass spectrometry analysis and scanning electron microscopy images of the surface, it was confirmed that the coating layer was successfully protected from the reactive electrolyte during storage at 90°C. In contrast, the surface of the pristine sample was severely damaged after storage.     

Influence of operating temperature on CO<Subscript>2</Subscript>-NH<Subscript>3</Subscript> reaction in an aqueous solution

Although aqueous ammonia solution has been focused on the removal of CO₂ from flue gas, there have been very few reports regarding the underlying analysis of the reaction between CO₂ and NH₃. In this work, we explored the reaction of CO₂-NH₃-H₂O system at various operating temperatures: 40 °C, 20 °C, and 5 °C. The CO₂ removal efficiency and the loss of ammonia were influenced by the operating temperatures. Also, infrared spectroscopy measurement was used in order to understand the formation mechanism of ion species in absorbent, such as NH₂COO⁻, HCO₃⁻, CO₃²⁻, and NH₄⁺, during CO₂, NH₃, and H₂O reaction. The reactions of CO₂-NH₃-H₂O system at 20 °C and 40 °C have similar reaction routes. However, a different reaction route was observed at 5 °C compared to the other operating temperatures, showing the solid products of ammonium bicarbonates, relatively. The CO₂ removal efficiency and the formation of carbamate and bicarbonate were strongly influenced by the operating temperatures. In particular, the analysis of the formation carbamate and bicarbonate by infrared spectroscopy measurement provides useful information on the reaction mechanism of CO₂ in an aqueous ammonia solution.     

Enhanced electrochemical properties of fluoride-coated LiCoO<Subscript>2</Subscript> thin films

The electrochemical properties of fluoride-coated lithium cobalt oxide [LiCoO₂] thin films were characterized. Aluminum fluoride [AlF₃] and lanthanum fluoride [LaF₃] coating layers were fabricated on a pristine LiCoO₂ thin film by using a spin-coating process. The AlF₃- and LaF₃-coated films exhibited a higher rate capability, cyclic performance, and stability at high temperature than the pristine film. This indicates that the AlF₃ and LaF₃ layers effectively protected the surface of the pristine LiCoO₂ film from the reactive electrolyte.     

Comparative study of the preparation and electrochemical performance of LiNi<Subscript>1</Subscript><Subscript>/2</Subscript>Mn<Subscript>1/2</Subscript>O<Subscript>2</Subscript> electrode material for rechargeable lithium batteries

Positive electrode material LiNi_1/2Mn_1/2O₂ was synthesized via the carbonate co-precipitation method and the hydroxide precipitation route to study the effects of the precursor on its structural and electrochemical properties. The results of X-ray diffraction and Rietveld refinement show that the carbonate precursor of Ni²⁺ and Mn²⁺ exhibits one phase at a pH of 8.5, while the hydroxide deposit separates into Ni(OH)₂ and Mn(OH)₂ phases under the same experimental conditions. LiNi_1/2Mn_1/2O₂ material prepared from the hydroxide precursor shows 8.9% Li/Ni exchange and a large capacity loss of 11.3% in the first 10 cycles. By contrast, more uniform distribution of transition metal ions and stable Mn²⁺ in the carbonate precursor contribute to only 7.8% Li/Ni disorder in the obtained LiNi_1/2Mn_1/2O₂, which delivers a reversible capacity of about 182 mAh g⁻¹ at a current rate of 14 mA g⁻¹ between 2.5 and 4.8 V.     

Application of ZnO and TiO<Subscript>2</Subscript> nanoparticles coated onto montmorillonite in the presence of H<Subscript>2</Subscript>O<Subscript>2</Subscript> for efficient removal of cephalexin from aqueous solutions

This study considers the feasibility of uptake of cephalexin, an emerging contaminant, from aqueous solutions by using green local montmorillonite (GLM), montmorillonite coated with ZnO (ZnO/GLM) and montmorillonite coated with TiO₂ (TiO₂/GLM) in the presence of H₂O₂. Batch adsorption experiments were carried out as a function of pH, initial concentration of the cephalexin, adsorbent dosage, contact time, and temperature. Finally, the adsorbents were characterized by XRD, SEM and FTIR analyses. XRD patterns showed dramatic changes in the adsorbents after loading with the nanoparticles, confirming successful placing of the nanoparticles onto GLM. The GLM mineral surface after nanoparticle loading appears to be fully exposed and more porous with irregular shapes in particles diameters of 1-50 microns. FTIR analyses also confirmed dramatic changes in surface functional groups after modification with these nanoparticles. The results showed that the removal efficiency of cephalexin was better at lower pH values. Totally, the removal efficiency increased with increase in adsorbent dosage and contact time and decreased with concentration and temperature increase. The thermodynamics values of ΔG ^o and ΔH ^o revealed that the adsorption process was spontaneous and exothermic. In isotherm study, the maximum adsorption capacities (qm) were obtained to be 7.82, 17.09 and 49.26 mg/g for GLM, ZnO/GLM and TiO₂/GLM, respectively. Temkin constant (B _T ) showed that adsorption of cephalexin from solution was exothermic for all three adsorbents.     

Characteristics of phosphate adsorption on ferric hydroxide synthesized from a Fe<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)<Subscript>3</Subscript> aqueous solution discharged from a hydrometallurgical process

Ferric hydroxide adsorbent was prepared by a chemical treatment process with H₂O₂, NaOH, and aeration from a Fe₂(SO₄)₃ aqueous solution as a side product discharged from the hydrometallurgical process used to extract neodymium. The ferric hydroxide was used as an adsorbent to prevent eutrophication in water. At the time of synthesis, the most important process variable is the pH condition, which, in this experiment, was changed from pH 3 to 13. The cost of synthesizing ferric hydroxide was sharply reduced by using ferric sulfate, which is considered a side product of the aforementioned hydrometallurgical process, as a starting material, and an adsorbent with high adsorption ability was prepared by controlling the pH level. Microstructural characterization of the synthesized ferric hydroxide revealed particles with a specific surface area of 194.2 m²/g and an average pore diameter of 2.66 nm at pH 6 and 298 K. A column-type packed-bed adsorption experiment was conducted under the following conditions: a flow rate of 0.567 BV/min (3.2 mL/min), 298 K, and atmospheric pressure. The results of the adsorption performance test indicated that the adsorption efficiency of phosphate at concentrations of 10 ppm was 100% at a flow rate of 0.567 BV/min within a contact time of 2 min, and the maximum adsorption capacity for phosphate ions was 65 mg/g.     

Improved performances of mechanical-activated LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript>/MWNTs cathode for aqueous rechargeable lithium batteries

LiMn₂O₄/multi-walled carbon nanotubes (MWNTs) composite was synthesized by mechanical activation reaction followed by a heat-treatment (500 °C). The LiMn₂O₄ and LiMn₂O₄/MWNTs as cathodes were investigated in 1 M Li₂SO₄ by cyclic voltammetry (CV), galvanostatic charge/discharge (GC), and electrochemical impedance spectroscopy (EIS). The LiMn₂O₄/MWNTs cathode delivered higher discharge capacity (117 mAh g⁻¹) than LiMn₂O₄ (84.6 mAh g⁻¹). Furthermore, the results from EIS showed that LiMn₂O₄/MWNTs had a faster kinetic process for lithium ion intercalation/de-intercalation than LiMn₂O₄. Besides, LiMn₂O₄/MWNTs had better cycling stability and rate capability than LiMn₂O₄, which was confirmed by GC testing. SEM images showed that a three-dimensional network structure was formed during the mechanical activation, giving a decrease of particle size.     

Phase transitions and structural mechanisms of the formation of LiCoO<Subscript>2</Subscript> polymorphic modifications

The structural mechanisms of formation of the low-symmetry phases of the LiCoO₂ compound from the praphase with a sodium chloride structure are investigated in the framework of the Landau phenomenological theory of phase transitions. The possibility of forming new modifications of the LiCoO₂ compound is predicted. The calculated structures of some possible low-symmetry phases of lithium cobaltite are described, and the possible phase diagrams are calculated. It is demonstrated that the most stable modifications of the LiCoO₂ compound (the spinel-like and rhombohedral modifications) can transform into each other through a first-order phase transition.     

A thermodynamic study of the Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-H<Subscript>2</Subscript>-CO system

The equilibrium composition of the Fe₂O₃-H₂-CO system depending on temperature and pressure was calculated by the methods of chemical thermodynamics at different molar ratios between the system components. It was found that the equilibrium composition of the mixtures formed in this system mainly depends on ratios between the system components. The effect of the partial pressures of H2 and CO on the equilibrium composition of products in the Fischer-Tropsch synthesis was determined.     

Simultaneous absorption of CO<Subscript>2</Subscript> and SO<Subscript>2</Subscript> into aqueous AMP/NH<Subscript>3</Subscript> solutions in binary composite absorption system

To enhance the absorption rate for CO₂ and SO₂, aqueous ammonia (NH₃) solution was added to an aqueous 2-amino-2-methyl-1-propanol (AMP) solution. The simultaneous absorption rates of AMP and a blend of AMP+ NH₃ for CO₂ and SO₂ were measured by using a stirred-cell reactor at 303 K. The process operating parameters of interest in this study were the solvent and concentration, and the partial pressures of CO₂ and SO₂. As a result, the addition of NH₃ solution into aqueous AMP solution increased the reaction rate constants of CO₂ and SO₂ by 144 and 109%, respectively, compared to that of AMP solution alone. The simultaneous absorption rate of CO₂/SO₂ on the addition of 1 wt% NH₃ into 10 wt% AMP at a p _A1 of 15 kPa and p _A2 of 1 kPa was 5.50×10⁻⁶ kmol m⁻² s⁻¹, with an increase of 15.5% compared to 10 wt% AMP alone. Consequently, the addition of NH₃ solution into an aqueous AMP solution would be expected to be an excellent absorbent for the simultaneous removal of CO₂/SO₂ from the composition of flue gas emitted from thermoelectric power plants.     

Synthesis and properties of the composite ceramics from nanocrystalline Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-30% Y<Subscript>0.1</Subscript>Zr<Subscript>0.9</Subscript>O<Subscript>2</Subscript> prepared from a water-alcohol solution

The hydrogel of the mixed oxide Al₂O₃-30% Y_0.1Zr_0.9O₂ was prepared by precipitation of ammonia from a water-alcohol mixture (1 : 5). The Al₂O₃-30% Y_0.1Zr_0.9O₂ compound thus synthesized was characterized using differential scanning calorimetry, transmission electron microscopy, and the BET adsorption method. The obtained sample consisted of spherical particles with an average size of 16–20 nm and a specific surface area of 167 m²/g. The Al₂O₃-30% Y_0.1Zr_0.9O₂ powder was pressed at 300 MPa and then calcinated at 1600°C for 2 h in air. The topographic and structural features of the prepared ceramics were determined using atomic force microscopy and X-ray electron probe microanalysis. The porosity, the Vickers microhardness, and the tensile strength were determined by mercury porometry.     

Photoreduction of CO<Subscript>2</Subscript> into CH<Subscript>4</Subscript> using Bi<Subscript>2</Subscript>S<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> double-layered dense films

Nano-sized bismuth sulfide (Bi₂S₃) and titanium dioxide (TiO₂) with the orthorhombic and anatase tetragonal structures, respectively, were synthesized for application as catalysts for the reduction of carbon dioxide (CO₂) to methane (CH₄). Four double-layered dense films were fabricated with different coating sequences—TiO₂ (bottom layer)/Bi₂S₃ (top layer), Bi₂S₃/TiO₂, TiO₂/Bi₂S₃: TiO₂ (1 : 1) mix, and Bi₂S₃: TiO₂ (1 : 1) mix/Bi₂S₃: TiO₂ (1 : 1) mix—and applied to the photoreduction of CO₂ to CH₄; the catalytic activity of the fabricated films was compared to that of the pure TiO₂/TiO₂ and Bi₂S₃/Bi₂S₃ doubled-layered films. The TiO₂/Bi₂S₃ double-layered film exhibited superior photocatalytic behavior, and higher CH₄ production was obtained with the TiO₂/Bi₂S₃ double-layered film than with the other films. A model of the mechanism underlying the enhanced photoactivity of the TiO₂/Bi₂S₃ double-layered film was proposed, and it was attributed in effective charge separation.     

Structure of an atmospheric-pressure H<Subscript>2</Subscript>/O<Subscript>2</Subscript>/N<Subscript>2</Subscript> flame doped with iron pentacarbonyl

This paper presents the measurement and simulation data on the thermal and chemical structure of an atmospheric-pressure premixed H₂/O₂/N₂ flame doped with iron pentacarbonyl Fe(CO)₅. Soft ionization molecular beam mass spectrometry was used to measure concentration profiles of the combustion products of iron pentacarbonyl: Fe, FeO₂, FeOH, and Fe(OH)₂. A comparison of experimental and simulated concentration profiles showed that they are in satisfactory agreement for FeO₂ and Fe(OH)₂ and differ significantly for Fe and FeOH. Thus, the previously proposed kinetic model for the oxidation of iron pentacarbonyl was tested and it was shown that the mechanism needs further elaboration.     

Investigation into the formation of phases with a Ba<Subscript>2</Subscript>Ti<Subscript>9</Subscript>O<Subscript>20</Subscript>-type structure in the BaO-TiO<Subscript>2</Subscript> and BaO-SrO-TiO<Subscript>2</Subscript> systems

The mechanism of formation of barium titanate Ba₂Ti₉O₂₀ in the BaO-TiO₂ and BaO-SrO-TiO₂ systems is investigated using initial mixtures prepared by three methods, namely, mechanical grinding of the initial reactants, coprecipitation from aqueous solutions of salts, and the sol-gel technique. It is established that, irrespective of the preparation procedure, the formation of Ba₂Ti₉O₂₀ proceeds through the formation of the intermediate phases BaTi₄O₉ and BaTi₅O₁₁. The nature of the intermediate phases is determined by the homogeneity and dispersion of the initial mixture, as well as by the stability of the intermediate phase. The most optimum conditions for the synthesis of Ba₂Ti₉O₂₀ are provided by the formation of BaTi₅O₁₁ as an intermediate phase upon heat treatment of the coprecipitation products in the nanocrystalline state. The metastability and structural defects in the BaTi₅O₁₁ intermediate phase encourage a decrease in the temperature of the final heat treatment by 100–150°C in the course of the preparation of Ba₂Ti₉O₂₀ single-phase ceramics.     

A study on the synthesis of water-soluble Sb<Subscript>2</Subscript>S<Subscript>3</Subscript>

Water-soluble Sb₂S₃ sub-microspheres were synthesized by aqueous-phase arrested precipitation using mercaptoacetic acid as capping agent and thioacetamide (TAA) as sulfur source. The effects of the experimental conditions, such as temperature, sulfur source, reactants concentration and reaction time, on the shapes, structures and properties of the products were studied. FESEM, TEM showed the products have uniform size distribution. In addition, ultraviolet-visible spectrophotometry (UV-vis) and photoluminescence (PL) showed the resulting products have excellent optical properties.     

Investigation into the phase formation in the ZrO<Subscript>2</Subscript>-CeO<Subscript>2</Subscript> system

Nanopowders of solid solutions with different compositions are prepared in the zirconia-enriched region of the ZrO₂-CeO₂ system. The crystallization of these powders and the formation of the monoclinic, cubic, and tetragonal solid solutions of the composition (Zr_{1 – x} Ce_x)O₂ are investigated. It is found that the unit cell parameters of the solid solutions increase as the cerium content increases. This confirms the fact that cerium ions [r(Ce⁴⁺) = 1.11 ] substitute for zirconium ions [r(Zr⁴⁺) = 0.98 ] in these solid solutions. The average size of crystallites of the solid solutions under investigation increases from 5 to 60 nm in the temperature range 500–1200°C.Original Russian Text Copyright © 2005 by Fizika i Khimiya Stekla, Panova, Glushkova, Nefedova.     

Interaction of O<Subscript>2</Subscript>, O<Subscript>3</Subscript>, and H<Subscript>2</Subscript>O<Subscript>2</Subscript> with an activated carbon

The results of the modification of AG-OV-1 activated carbon under various conditions (by atmospheric oxygen at elevated temperatures and by hydrogen peroxide or ozone) are given. The effect of the used modifier on changes in the porosity, surface state, and adsorption capacity of activated carbon is evaluated.