Morphology and photoluminescence of BaAl12O19:Mn2+ green phosphor prepared by flux method

This paper reports that the green phosphor BaAl11.9O19:0.1Mn2+ is prepared by a flux assisted solid state reaction method.The effect of flux systems on the crystal structure,morphology and luminescent properties of the phosphor are studied in detail.The samples are characterized by the application of x-ray diffraction patterns,scanning electron microscopy patterns,luminescent spectra and decay curves.The results show that a pure phase BaAl12O19 can be achieved at the firing temperature above 1300℃ by adding the proper flux system,the firing temperature is reduced at least 200℃ in comparison with the conventional solid state reaction method.Maximum photoluminescence emission intensity is observed at 517 nm for(AlF3+Li2CO3) flux system under vacuum ultraviolet region(147 nm) excitation.The photoluminescence emission intensity and the decay time of these phosphor is found to be more superior to that of the corresponding sample prepared by the conventional solid state reaction method implying the suitability of this route for the preparation of display device worthy phosphor materials.     

Physico-chemical properties and possible photocatalytic applications of titanate nanotubes synthesized via hydrothermal method

Titanate nanotubes (TNTs) were prepared from TiO₂ P25 via hydrothermal method. The reaction temperature was 130 or 140 °C and the reaction time was 24 or 48 h. The samples were characterized by transmission electron microscopy, X-ray diffraction, thermogravimetry and N₂ adsorption as well as Raman, FTIR-DRS and UV-vis/DR spectroscopy. The obtained samples exhibited similar properties, regardless of the preparation temperature and time. The most notable difference between properties of TNTs prepared under different conditions was observed in case of BET surface area, which was increasing from 386 to 478 m²/g along with increasing the reaction time and temperature. Based on TEM, XRD and TG measurements we have suggested that the structure of TNTs was H₂Ti₂O₄(OH)₂. The TEM and Raman spectroscopy measurements showed that the obtained products contained also low amount of anatase phase. The TNTs exhibited no photoactivity towards degradation of model azo dye Acid Red 18. However, TNTs were successfully applied for photocatalytic generation of CH₄ and H₂ in a solution of acetic acid. The amount of methane produced with application of TNTs synthesized at 140 °C was about 2.5 times higher than that generated with use of TiO₂ P25. To the best of our knowledge this is a first report on the photocatalytic generation of hydrocarbons using TNTs in the current state of the art.     

Niobian iron oxides as heterogeneous Fenton catalysts for environmental remediation

Heterogeneous Fenton or Fenton-like reagents consist of a mixture of an iron-containing solid matrix and a liquid medium with H₂O₂. The Fenton system is based on the reaction between Fe^2?+? and H₂O₂ to produce highly reactive intermediate hydroxyl radicals (^???OH), which are able to oxidize organic contaminants, whereas the Fenton-like reaction is based on the reaction between Fe^3?+? and H₂O₂. These heterogeneous systems offer several advantages over their homogeneous counterparts, such as no sludge formation, operation at near-neutral pH and the possibility of recycling the iron promoter. Some doping transition cations in the iron oxide structure are believed to enhance the catalytic efficiency for the oxidation of organic substrates in water. In this work, goethites synthesized in presence of niobium served as precursors for the preparation of magnetites (niobian magnetites) via chemical reduction with hydrogen at 400°C. These materials were used as Fenton-like catalysts. Both groups of (Nb, Fe)-oxide samples were characterized by ⁵⁷Fe Mössbauer spectroscopy at 298 K. The results show that increasing niobium contents raise the catalytic potential for decomposition of methylene blue, which was, in this work, used as a model molecule for organic substrates in water.     

Ultrasound assisted co-precipitation synthesis and catalytic performance of mesoporous nanocrystalline NiO-Al2O3 powders

Mesoporous nanocrystalline NiO-Al₂O₃ powders with high surface area were synthesized via ultrasound assisted co-precipitation method and the potential of the selected samples as catalyst was investigated in dry reforming reaction for preparation of synthesis gas. The prepared samples were characterized by N₂ adsorption (BET), X-ray diffraction (XRD), Temperature programmed reduction and oxidation (TPR, TPO) and scanning electron microscopy (SEM) techniques. The effects of pH, power of ultrasound irradiation, aging time and calcination temperature on the textural properties of the catalysts were studied. The sample prepared under specified conditions (pH10, 70 W, without aging time and calcined at 600 °C) exhibited the highest surface area (249.7 m² g⁻¹). This catalyst was calcined at different temperature and employed in dry reforming of methane and the catalytic results were compared with those obtained over the catalysts prepared by impregnation and co-precipitation methods. The results showed that the catalyst prepared by ultrasound assisted co-precipitation method exhibited higher activity and stability with lower degree of carbon formation compared to catalysts prepared by co-precipitation and impregnation methods.     

The low temperature water formation reaction on Pt(111): A static SIMS and TDS study

The formation of water by the reaction of preadsorbed oxygen with hydrogen on a Pt(111) surface has been characterized, using secondary ion mass spectroscopy, below the desorption temperature of H₂O (180 K). The concentration of chemisorbed water was monitored during the reaction by following the SIMS H₃O⁺ signal. Reaction profiles were measured over a temperature range of 120 to 153 K, and an H₂ pressure range of 10^-9 to 10^-6 Torr. Under all conditions the reaction profiles were characterized by an induction time, a region of rapid reaction, and finally a steady decline in the rate. In the rapid region, an overall activation energy of 2.9 ± 0.3 kcalmol^-1 and a half-order H₂ pressure dependence were observed. At low initial oxygen concentrations the induction time increased and the maximum rate decreased. The reaction was slow in the absence of gas phase hydrogen, even when the surface coverage of hydrogen was relatively high. Water and hydrogen thermal desorption spectra, measured after stopping the reaction by removal of gas phase hydrogen, were complex functions of the H₂ exposure, exhibiting several peaks between 170 and 400 K. However, after an exposure large enough to drive the reaction to completion, only one H₂O peak at 173 K and one H₂ peak at 350 K were observed. The results indicate that only a fraction of the total H(a) on the surface was readily available for reaction during H₂ exposure at T ? 153 K. the remainder either recombined to form H₂ or reacted with O(a) during the thermal desorption ramp. There is good evidence for a surface rearrangement during the induction period. A model is proposed which involves the formation of water clusters that accelerate the rate.     

On Line Dissolution of ZnS For Sulfide Determination in Stabilized Water Samples with Zinc Acetate,Using Spectrophotometry by Methylene Blue Method

Abstract

Stabilization of sulfide as zinc sulfide is a strategy widely used in batch analysis of this ion in water. A FIA/spectrophotometry system to determine sulfide in stabilized water samples is proposed in this paper. The methodology is based on the formation of methylene blue by the reaction of H₂S with a mixture of Fe³⁺ solution and N,N-dimethyl-p-phenylenediamine (DMPD) in acidic medium. In the system, the sample (480 μL) containing stabilized sulfide (as ZnS slurry) is injected in a carrier stream formed by mixing acidic Fe³⁺ and DMPD. In the reactor coil of 1280 μL, the sulfide is drifted by acid used in the preparation of solutions, releasing H₂S that reacts with Fe³⁺ and DMPD forming methylene blue. The absorbance is measured at 662 nm. The performance of the FIA system was optimized in relation to chemical and flow parameters. The stability of the solutions were studied throughout the period of the experiment. The results did not show any loss of sulfide over a 7 day period. However, in complex matrices an analysis by using the standard addition method is recommended. The analysis of effluent sample through the time showed good agreement between the results obtained each day. The developed system presented the following figures of merit: detection limit of 50 μg L^?1; RSD of 6% at 0.5 μg mL^?1 (using ultrasonic homogenization) and analytical throughput of 60 samples per hour.     

ZnFe2O4的固相法和水热法制备及其电化学性能研究

本文用固相反应法和水热法制备了ZnFe₂O₄材料,X射线衍射(X-ray diffraction, XRD)表明制备出来的ZnFe₂O₄为尖晶石结构,表面形貌测试 (scanning electron microscopy, SEM) 显示两种方法制备的材料的平均粒径分别为500 nm和200 nm.比表面积测试结果表明,两种方法制备的样品的比表面积分别为136.7 m² g^{-1关键词： 2O₄')" href="#">ZnFe₂O₄ 尖晶石结构 电化学性能 锂离子电池}     

New insight on kinetics of catalytic decomposition of hydrogen peroxide on ferrihydrite: Based on the preparation procedures of ferrihydrite

The heterogeneous catalytic reaction of H₂O₂ with iron oxides is an important reaction for the environment since both H₂O₂ and iron oxides are common constituents of natural and atmospheric waters. In this work, three ferrihydrites, labeled Fh-1, -2 and -3, were prepared by different procedures. Fh-1 was prepared by adding alkali solution to ferric solution under stirring. In the preparation of Fh-2, the mixing procedure of the two solutions was reversed. Fh-3 was obtained by adding alkali solution and ferric solution simultaneously into a certain amount of water. The heterogeneous catalytic reaction of H₂O₂ with three ferrihydrites in aqueous solution was investigated in detail. The results demonstrated that the apparent reaction rate was affected by the preparation procedure of ferrihydrite besides pH, temperature and the dose of catalyst. The activation energy of the decomposition reaction of H₂O₂ was determined to be 76.13, 59.41 and 68.05 kJ mol^?1 for Fh-1, -2 and -3, respectively. The activation enthalpy of the reaction were determined to be 73.59, 56.56 and 65.76 kJ mol^-1 and the activation entropy of the reaction were determined to be ?69.65, ?119.67 and ?90.58 J mol^?1 K^?1, respectively.     

Effects of sintering temperature and atmosphere on magnetism in Mn-doped TiO2 bulk samples

Magnetic properties have been investigated on Mn doped TiO₂(Ti_0.98Mn_0.02O₂) bulk samples prepared by solid state reaction, which were sintered at different temperature ranging from 450 ^°C to 900 ^°C in air and argon atmosphere, respectively. The results show that the magnetic properties were strongly dependent on the sintering temperature and atmosphere. For samples sintered in air, the magnetization initially increase with the increase of sintering temperature up to 600 ^°C and thereafter it decrease. While the magnetization of samples sintered in argon atmosphere decreases monotonically with the increase of sintering temperature. Furthermore, for samples sintered at 600 ^°C in air, the magnetic susceptibility exhibits a dominant Curie-Weiss behaviour and no magnetic transition is observed over the temperature range from 10 to 300 K. In contrast, for samples sintered in argon atmosphere, besides the magnetic transition near 45 K perhaps caused by Mn₃O₄, another magnetic transition appears near room temperature.     

Study on the Separation of Carrier-Free Yttrium-90 from Strontium-90

The separation of carrier-free ⁹⁰Y from ⁹⁰Sr by solvent extraction with di-(2-ethylhexyl) phosphoric acid (HDEHP) in dodecane has been investigated in this study. The extraction equilibrium time, the effect of temperature, concentration of extractant, and hydrochloric acid concentration on this extraction system were examined. Based on the studies, the chemical procedure for the separation of carrier-free ⁹⁰ Y from its parent ⁹⁰Sr have been established. The chemical yield of ⁹⁰Y is about 80%. Meanwhile, the ⁹⁰Sr impurity is less than 1×10^?6% and the trace of extractant presented in the final product can be removed by fumed with HNO₃. Consequently, the preparation of millicurie of ⁹⁰Y is quite satisfactory for the adsorption in microsphere resin for radiotherapy applications.     

Equilibrium of 1:2:3 CLBLCO superconductors with oxygen: reaction equation,thermodynamics and improvement of homogeneity

Equilibrium of 1:2:3 superconductors (Ca_xLa_1−x)(Ba_1.75−xLa_0.25+x)Cu₃O_y (this compound has in the past variously denoted as CLBLCO, CLBCO or CaLaBaCuO) with oxygen was studied for x=0.1 and x=0.4 in the temperature range of 150–950 °C under 1 atm. O₂. The main process is the reversible reaction −Cu₃²⁺O_6.625+0.25O₂=−Cu₂²⁺Cu³⁺O_7.125 which is completed with the formation of one Cu³⁺. The enthalpy (in kJ/mol CLBLCO) and entropy (in J(mol CLBLCO)⁻¹K⁻¹) of this reaction were calculated from the temperature dependence of the equilibrium constant. The values are ΔH=−33.1 and ΔS=−29.9 for x=0.1 and ΔH=−49.4 and ΔS=−42.7 for x=0.4.It was found that the equilibrium of ceramic pellet of CLBLCO with oxygen cannot be practically achieved below 300 °C while the equilibrium for powder is achieved even at 200 °C. Low rate of reaction of CLBLCO with oxygen causes the problem in low temperature equilibration. In contrast, diffusion of oxygen ions in the ceramics is observed even at 200 °C. This diffusion proceeds without the change of the oxygen content and may be applied in order to improve the homogeneity of the distribution of oxygen ions.     

Conductivity of Wigner liquid

The conductivity of two-dimensional electron systems with low carrier concentration is considered on the basis of the previously suggested model (Fermi liquid with a soft mode) under the assumption that the equilibrium in each of the (fermion and boson) subsystems is established faster than the impurity relaxation and the relaxation between the subsystems (hydrodynamic approximation). The conductivity of the system depends on three characteristic times: τ₁(τ₂) is determined by the fermion (boson) impurity scattering and τ₁₂ is determined by the friction between the subsystems; the respective temperature dependences are obtained. The conductivity is related to the relaxation time τ in the usual way, and τ obeys the relationship τ^?1=τ ₁ ^?1 +(τ₂+τ₁₂)^?1. It follows from the results obtained that the resistivity of pure samples should increase with temperature and tend towards saturation.     

Fluorimetric Method Based on Diazotization-Coupling Reaction for Determination of Clenbuterol

A novel fluorimetric method based on diazotization-coupling reaction (DCR) for the determination of clenbuterol is described. In acidic solution, clenbuterol was first diazotized with sodium nitrite, followed by coupling with bisphenol A to produce an azo-compound in NH₃- NH₄Cl buffer. It has found the diazotized clenbuterol- bisphenol A- NH₃- NH₄Cl (DCBN) system has strong fluorescence efficiency compare with the bisphenol A solution. There is a linear relationship between the increased intensity of the fluorescence emission spectra (λ_ex/λ_em?=?276 nm/306 nm) and the concentration of clenbuterol. The effects of the amount of sodium nitrite, diazo reaction time, the amount of bisphenol A, coupling reaction time and coupling reaction temperature have been examined. Under the optional conditions, clenbuterol can be determined over the concentration range of 0.02 to 2.0 μg mL^?1 with a correlation coefficient of 0.9953. The detection limit is 0.01 μg mL^?1 at a signal-to-noise ratio of 3. The relative standard deviation (RSD) for 11 repetitive determinations of 0.9 μg mL^?1 clenbuterol is 0.22 %. The utility of this method was demonstrated by determining clenbuterol in meat samples.     

Microstructure of LaCoO3 prepared by freeze-drying of metal-citrate precursors revealed by EPR

Two methods for the preparation of LaCoO₃ samples were used: thermal decomposition of La-Co citrate precursors obtained by freeze-drying of the corresponding solutions and by a solid state reaction. Microstructural characterization was made by electron paramagnetic resonance spectroscopy (EPR). For assignment of the EPR signals, La_1−xSr_xCoO₃ samples were used as EPR references. The LaCoO₃ oxides prepared from citrates and by a solid state reaction were shown to differ in respect of the mean oxidation state of the cobalt ions, the specific surface area and the particle morphology. EPR spectroscopy reveals for ex-citrate LaCoO₃ ferromagnetic Co³⁺ and Co⁴⁺ coupled ions. For LaCoO₃ samples obtained by a solid state reaction, EPR permits detecting Co₃O₄ impurities only.     

Role of water contamination within the GC column of a GasBench II peripheral on the reproducibility of 18O/16O ratios in water samples

The GasBench II peripheral along with MAT 253 combination provides a more sensitive platform for the determination of water isotope ratios. Here, we examined the role of adsorbed moisture within the gas chromatography (GC) column of the GasBench II on measurement uncertainties. The uncertainty in ¹⁸O/¹⁶O ratio measurements is determined by several factors, including the presence of water in the GC. The contamination of GC with water originating from samples as water vapour over a longer timeframe is a critical factor in determining the reproducibility of ¹⁸O/¹⁶O ratios in water samples. The shift in isotope ratios observed in the experiment under dry and wet conditions correlates strongly with the retention time of analyte CO₂, indicating the effect of accumulated moisture. Two possible methods to circumvent or minimise the effect of adsorbed water on isotope ratios are presented here. The proposed methodology includes either the regular baking of the GC column at a higher temperature (120 °C) after analysis of a batch of 32 sample entries or conducting the experiment at a low GC column temperature (22.5 °C). The effects of water contamination on long-term reproducibility of reference water, with and without baking protocol, have been described.     

Effect of preservation on the δ13C value of dissolved inorganic carbon in different types of water samples

Recent studies have shown that the stable carbon isotope compositions of dissolved inorganic carbon (δ¹³C_DIC) of water samples preserved with HgCl₂ and CuSO₄ vary. Furthermore, mercury and cuprum compounds are toxic to the human or biological system and require proper waste disposal. To test the effect of preservation on the δ¹³C value of DIC in different types of water samples, a set of water samples with different DIC concentrations was preserved using different methods, including preserving with inhibitors (CuSO₄ or HgCl₂), preserving under frozen conditions, filtering through a 0.4 μ m paper filter, and the DIC species precipitated in the form of solid BaCO₃. Our results show that δ¹³C_DIC values of the samples preserved with CuSO₄ and HgCl₂ become more positive with increased storage time. The δ¹³C_DIC of the water samples preserved under frozen conditions and the precipitated DIC as BaCO₃ are also more positive than original water samples. However, the δ¹³C values were relatively stable for up to 90 days in all water samples filtered through the 0.4 μ m paper filter and stored under cool conditions (0–4 °C). Therefore, we suggest that the better method for the storage of water samples is to filter the samples through a 0.4 μ m paper filter while out in the field and preserve them under cool conditions, thereby avoiding the use of preservatives.     

Structural and magnetic studies of the Zn-substituted magnesium ferrite chromate

The formation of iron oxide nanoparticles in course of a sol-gel preparation process was traced by UV/Vis and ⁵⁷Fe Mössbauer absorption spectroscopy. Samples were extracted at different stages of the reaction. While spectra measured on samples extracted at low reactor temperatures showed the starting materials Fe(acac)₃ diluted in benzyl alcohol undergoing slow paramagnetic relaxation, a sample extracted at a reactor temperature of 180 °C gave clear evidence for emerging iron oxide nanoparticles. A prolonged stay at 200 °C results in a complete transformation from Fe(acac)₃ to maghemite nanoparticles.     

Evaluation of Water Removal and Memory Effect in 13CO2 Breath Tests by Isotope Ratio Mass Spectrometry

The usefulness of different ways of water removal in off-line sample preparation of human breath samples for ¹³CO₂ breath tests was examined and compared. Cryogenic water trapping and water removal with common desiccants like silicagel blue, Mg(ClO₄)₂, and molecular sieves were checked for reliability and reproducibility. With silicagel blue and Mg(ClO₄)₂ memory effects for ¹³C content were observed. The use of molecular sieve 4 Å and 5 Å led to tremendous carbon isotope fractionation. Molecular sieve 3 Å was found to be an excellent alternative to the established use of Mg(ClO₄)₂ and of cryogenic water trapping.     

The Possibility of the Use of Coprecipitation with Lanthanum Fluoride for Preparation of Samples for Alpha-Spectrometric Determination of Plutonium

At present time the content of ²³⁹Pu, ²³⁸Pu especially in biological and environmental samples and nuclear fuels is frequently determinated. After radiochemical separation is plutonium usually electrodeposited on a metallic disk [1, 2]. Alpha-activity is then detected by silicon surface barrier detector.

The method of electrodeposition shows several disadvantages. The solution to be electrolyzed must have a definite composition, certain elements, e.g. iron, must not be present. The method is rather time-consuming and requires special equipment. Several other methods for preparation of samples using coprecipitations [3] or inorganic ionexchangers [4] have been studied. In this work was investigated the possibility of the use of coprecipitation of Pu³⁺ with LaF₃ for preparation of samples for alpha-speetroinetric determination of plutonium.     

Defect structure analysis of B-site doped perovskite-type proton conducting oxide BaCeO3 Part 1: The defect concentration of BaCe0.9M0.1O3−δ (M = Y and Yb)

By means of a high-temperature gravimetry, the defect chemical relationships between oxygen nonstoichiometry and water content in BaCe_0.9M_0.1O_3?δ (M = Y and Yb) were investigated as functions of partial pressure of oxygen, P(O₂), partial pressure of water vapor, P(H₂O), and temperature. Concentrations of protonic defect and that of oxygen vacancy strongly depend on P(H₂O) and temperature, while the dependences on P(O₂) were weak. The equilibrium constants of the water vapor incorporation reaction H₂O + V_O^??? + O_O^× = 2OH_O^? were determined. Concentrations of hole, [h^?], in the dry-atmospheres were determined by the weight gain by the incorporation of oxygen from the gas atmospheres. The [h^?] values increased with decreasing temperature. The [h^?] values were estimated to be about 2 to 3 orders of magnitude less than [OH_O^?] values measured in the wet-atmospheres.