Radioluminescence in ZnO

ZnO powders were obtained by proteic sol–gel process using zinc sulfate as the precursor. They have an energy gap of 3.3 eV and display a radioluminescence signal centered in 550 nm, which corresponds to 2.6 eV. This signal has appeared due to defects in the gap (energy sublevels) caused by the distortions in its crystalline structure, which result from the loss of sulfur at high temperature. These powders were characterized by radioluminescence, XRD, SEM, EDS and DTA/TG.     

A new processing method of CaZn2(OH)6·2H2O powders: Photoluminescence and growth mechanism

In this communication, we report on the formation of calcium hexahydroxodizincate dehydrate, CaZn₂(OH)₆·2H₂O (CZO) powders under microwave-hydrothermal (MH) conditions. These powders were analyzed by X-ray diffraction (XRD), Field-emission gum scanning electron microscopy (FEG-SEM), ultraviolet-visible (UV-vis) absorption spectroscopy and photoluminescence (PL) measurements. XRD patterns confirmed that the pure CZO phase was obtained after MH processing performed at 130 °C for 2 h. FEG-SEM micrographs indicated that the morphological modifications as well as the growth of CZO microparticles are governed by Ostwald-ripening and coalescence mechanisms. UV-vis spectra showed that this material have an indirect optical band gap. The pure CZO powders exhibited an yellow PL emission when excited by 350 nm wavelength at room temperature.     

Nanocrystalline hydroxyapatite powders by a chitosan–polymer complex solution route: Synthesis and characterization

Nanocrystalline hydroxyapatite (HAp) powders were successfully synthesized by a simple method using chitosan–polymer complex solution. To obtain HAp nanopowders, the prepared precursor was calcined in air at 400–800 °C for 2 h. The phase composition of the calcined samples was studied by X-ray diffraction (XRD) technique. The XRD results confirmed the formation of HAp phase with a small trace of monotite phase. With increasing calcination temperature, the crystallinity of the HAp increased, showing the hexagonal structure of HAp with the lattice parameter a in a range of 0.94030–0.94308 nm and c of 0.68817–0.68948 nm. The particle sizes of the powder were found to be 55.02–73.36 nm as evaluated by the XRD line broadening method. The chemical composition of the calcined powders was characterized by FTIR spectroscopy. The peaks of the phosphate carbonate and hydroxyl vibration modes were observed in the FTIR spectra for all the calcined powders. TEM investigation revealed that the prepared HAP samples consisted of rod-like nanoparticles having the particle size in the range of 100–300 nm. The corresponding selected-area electron diffraction (SAED) analysis further confirmed the formation of hexagonal structure of HAp.     

Structural characterization and activation energy of NiTiO3 nanopowders prepared by the co-precipitation and impregnation with calcinations

In this paper, we report on the formation of novel hexagonal NiTiO₃ nanopowders synthesized by the impregnation or co-precipitation methods through the thermal decomposition reaction of the precursors. The decomposition course was followed using differential thermal analysis (DTA) and thermogravimetric analysis (TGA) techniques. The intermediate decomposition products as well as the formed titanate were characterized using X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy. XRD patterns of the precursors calcined at 1000 °C showed the formation of the single ilmenite-type rhombohedral structure only with the impregnated precursor, while with the precipitated NiTiO₃ powders one it indicates the presence of some NiO and TiO₂ impurities. Transmission electron microscopy (TEM) exhibited loosely agglomerated hexagonal particles with uniform morphology having a size around 61 nm. The Brunauer-Emmett-Teller (BET) surface area measurements showed a type III isotherm with calculated surface area of 152 m²/g. The plot of ln σ_ac vs. temperature as a function of frequency indicates a semiconducting behavior with ferroelectric phase transition at 605 K. The calculated activation in the ferroelectric region is 0.93 eV suggests the predominance of hopping conduction mechanism. Kinetic analysis of TG data according to different integral methods showed that in the NiC₂O₄·2H₂O–TiO₂ precursor, the water molecules are coordinately bounded and the presence of TiO₂ reduces the activation energy needed to the oxalate decomposition reaction.     

Studies of dielectric characteristics of BaBi2Nb2O9 ferroelectrics prepared by chemical precursor decomposition method

BaBiNb₂O₉ (BBN) powders in the nanometer range were prepared by chemical precursor decomposition method (CPD). TG–DTA showed that precursor sample got freed from organic contaminants at 575 °C. XRD showed that a single phase with the layered perovskite structure of BBN was formed after calcining at 600 °C. No intermediate phase was found during heat treatment at and above 600 °C. The crystallite size (D) and the effective strain (η) were found to be 26 nm and 0.000867, respectively, while the particle size obtained from TEM was 28 ± 2 nm. SEM revealed that the average grain size after sintering at 900 °C for 4 h was ∼1.67 μm. A relative density of ∼93% was obtained using a two-step sintering process at moderate pressure. Dielectric and ferroelectric properties were investigated in the temperature range 50–500 °C and frequencies from 1 kHz to 5 MHz. Strong dispersion of the complex relative dielectric constant was observed including typical relaxor features such as shift of permittivity maximum with frequency and broadening of the peak maximum. The high dielectric constant of 545 measured at 100 kHz and other properties of BBN ceramics were compared to that of BBN prepared by other conventional methods and found to be superior.     

Solid-state synthesis of monazite-type compounds LnPO4 (Ln = La to Gd)

This work is devoted to the synthesis of monazite-type compounds LnPO₄ (with Ln = La, Ce, Pr, Nd, Sm, Eu and Gd) by solid–solid reaction between a lanthanide oxide and a phosphate precursor NH₄H₂PO₄. Starting mixtures and resulting powders were characterized by coupling different techniques, in particular thermal analysis, X-ray diffraction and MAS ³¹P NMR. Results are presented according to the valence state of the lanthanide element in its oxide form. The intermediate chemical reactions occurring during the firing of starting reagents are described for the first time in the case of monazite with one or several cations. It has been highlighted that the solid-state route is an efficient way in order to obtain very pure and very well crystallized monazite powder. Optimum synthesis conditions are 1350 °C–2 h. The synthesis of monazite powders containing several lanthanides appears to be more difficult, because all the lanthanides do not react at the same temperature, leading to the formation of heterogeneous powders.     

Low temperature synthesis of highly ion conductive Li7La3Zr2O12–Li3BO3 composites

Highly lithium ion conductive composites with Al-doped Li₇La₃Zr₂O₁₂ (LLZ) and amorphous Li₃BO₃ were prepared from sol–gel derived precursor powders of LLZ and Li₃BO₃. Precursor LLZ powders with cubic phase were obtained by a heat treatment of the precursor dried gel at 600 °C. Pellets of the mixture of the obtained LLZ and Li₃BO₃ were first held at 700 °C, and then successively sintered at 900 °C. Density of the sintered pellet with Li₃BO₃ was larger than that of the pellet without Li₃BO₃. From the TEM observation, the pellets were found to consist of cubic LLZ and amorphous Li₃BO₃. Total electrical conductivity of the obtained LLZ–Li₃BO₃ composite was 1 × 10^− 4 Scm^− 1 at 30 °C.     

Mesoporous germanium as anode material of high capacity and good cycling prepared by a mechanochemical reaction

Mesoporous Ge was prepared by mechanochemical reaction of GeO₂ and Mg powders followed by an etching process with HCl solution. It was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and charge–discharge measurement. With a pore-distribution concentrated around 10 nm, the product presents a BET surface area of 49.98 m²/g. When using as an anode material for lithium ion battery, the mesoporous Ge exhibits a reversible capacity of 950 mA h/g and retains a capacity of 789 mA h/g after 20 cycles at a current density of 150 mA/g. The cycleability is significantly improved compared with non-porous Ge.     

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.     

A novel approach for synthesis of nanocrystalline γ-LiAlO2 from spent lithium-ion batteries

Synthesis of nanocrystallite γ-LiAlO₂ from spent lithium-ion batteries has been investigated. XRD results show that γ-LiAlO₂ phase can be synthesized by thermal treatment of the cathode material over its aluminum sheet at 800–900 °C for 2 h. This is accompanied with the formation of Co₃O₄ and CoO phases as colored powders. SEM investigation revealed the formation of dense grains as coconut-like shape structure of γ-LiAlO₂ phase. Comparatively, reaction of chemical grade Al powder with LiOH in stoichiometric ratio at 800 °C gives γ-LiAlO₂ phase of cotton-like morphology.     

Producing metallic titanium through electro-refining of titanium nitride anode

Titanium nitride (TiN) was used as consumable anode to produce metallic titanium in molten salts. The electrochemical dissolution of TiN was investigated. It was found that nitrogen (N₂) was monitored at the anode during electrolysis. The titanium ion species was changed between Ti^2 + and Ti^3 + depending on the electrochemically dissolving potentials of TiN. Furthermore, the product on the cathode was analyzed using scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results show that pure titanium powders can be prepared by the TiN electro-refining in a molten salt bath.     

Preliminary investigation on the physicochemical properties of calcium ferrate(VI)

Calcium ferrate(VI) powders were synthesized from potassium ferrate(VI), and characterized by titration analysis, elemental analyzer, SEM, XRD, IR, TG and DSC. The results showed that the synthesized sample mainly consists of calcium ferrate(VI), and calcium ferrate(VI) may exist as CaFeO₄ · 2H₂O with a highest obtained purity of 74.9%. The relatively higher Fe(III) impurity and crystalloid water might be responsible for the poor stability of the calcium ferrate(VI) sample. The results of galvanostatic discharge experiments indicated that the calcium ferrate (VI) sample displays better intrinsic rate discharge capability and larger discharge capacity at lower temperatures (⩽15 °C).     

Synthesis and characterization of WO3 nanoparticles prepared by the precipitation method: Evaluation of photocatalytic activity under vis-irradiation

WO₃ nanoparticles were synthesized by the precipitation method varying the time employed in the formation of their precursor in aqueous media and the calcination temperature. The WO₃ crystallization process and morphology of the synthesized samples were followed by the XRD, TEM and SEM techniques. The effects of the calcination temperature on the surface area and optical properties of the WO₃ nanoparticles were also investigated. Nanoparticles with morphologies such as square and rectangular plates and ovoid forms were observed for the different experimental conditions. WO₃ nanoparticles with different morphologies were tested for the photocatalytic degradation of organic dyes. In general, the photocatalysts showed a capacity to bleach the dye solution in the following sequence: indigo carmine (IC) > rhodamine B (rhB) > congo red (CR). The extent of mineralization was determined by means of total organic carbon (TOC) measurements, which showed a satisfactory TOC reduction (93%, within 75 h) only for IC. This value was even better than the one concerning the P-25 Degussa reference.     

Synthesis and characterization of nanocrystalline tin oxide by sol–gel method

Nanocrystalline SnO₂ particles have been synthesized by a sol–gel method from the very simple starting material granulated tin. The synthesis leads a sol–gel process when citric acid is introduced in the solution obtained by dissolving granulated tin in HNO₃. Citric acid has a great effect on stabilizing the precursor solution, and slows down the hydrolysis and condensation processes. The obtained SnO₂ particles range from 2.8 to 5.1 nm in size and 289–143 m² g⁻¹ in specific surface area when the gel is heat treated at different temperatures. The particles show a lattice expansion with the reduction in particle size. With the absence of citric acid, the precursor hydrolyzes and condenses in an uncontrollable manner and the obtained SnO₂ nanocrystallites are comparatively larger in size and broader in size distribution. The nanocrystallites have been characterized by means of TG-DSC, FT-IR, XRD, BET and TEM.     

Elaboration of metallic compacts with high porosity for mechanical supports of SOFC

The development of third generation Solid Oxide Fuel Cells (SOFC) with metallic mechanical supports presents several advantages over that of ceramic stacks by offering a lower cost and longer lifetime of the stacks. As a consequence, it is necessary to prepare metallic porous compacts that remain stable at the operating temperature of the SOFC (700–800 °C) under reductive atmosphere. This paper presents an innovative process to elaborate iron, nickel and cobalt porous compacts. The process is based on the thermal decomposition of metal oxalate precursors with controlled morphology into metallic powders with coralline shape. Uniaxial compaction of such powders (without binder addition to the powders) under low uniaxial pressures (rising from 20 to 100 MPa) gave rise to green compacts with high porosity and good mechanical properties. After annealing at 800 °C under H₂ atmosphere, the compacts still present interconnected porosity high enough to allow sufficient gas flow to feed a SOFC single cell in hydrogen: the porosity rises from 25 to 50% for iron compacts, from 20 to 50% for cobalt compacts, and is higher than 40% for nickel compacts. Results from physicochemical characterization (XRD, SEM, gas permeation, Hg porosimetry) corroborated the process for SOFC application.     

Studies on Fe–Co spinel electrodes

FeCo₂O₄ spinel oxide pelleted electrodes were prepared from the respective powders, obtained by low-temperature coprecipitation method. X-ray diffraction studies suggest the coexistence of two spinel phases, with different a-cell parameters. The samples show semiconductor-type behaviour, in the range 530–340 K. The estimated activation energy for conduction is about 0.7 eV. These phases are stable, after being used as electrode materials, as the XRD and SEM/EDS results show. Cyclic voltammetry has been used to investigate the electrochemical behaviour of the FeCo₂O₄ electrodes in 1 mol dm⁻³ KOH aqueous solutions. The voltammetric data allowed finding out the redox reactions occurring at the electrode surface, namely Fe₃O₄·4H₂O/Fe(OH)₂ or Fe₃O₄/Fe₂O₃ and CoO₂/CoOOH by comparing the experimental results with those referred in the literature.     

Photoluminescence of La/Ti mixed oxides prepared using sol–gel process and their pCBA photodecomposition

La/Ti mixed oxides with weight ratios of 1:9, 2:8, 3:7, and 4:6 were prepared by sol–gel method. The photocatalytic activity of La/Ti oxides was evaluated based on the pCBA photodecomposition. The catalyst samples were characterized by XRD, TEM, DRS, BET, and photoluminescence (PL) spectra. Particles of the La/Ti-mixed oxides showed the diameter of about 7 nm. We found that 30% doping of lanthanum ions on the TiO₂ powders induced the highest pCBA (4-chlorobenzonic acid) photodecomposition in these experimental conditions. The order of its photoactivity was as following: 30 > 20 > 0 > 10 > 40 wt%, which was the same for PL tendency. Also, PL spectra intensity increased with calcination temperature from 500 to 600 °C, then decreased at 700 °C. Phtotcatalytic activity followed the trend of the PL spectra intensity. The modification of TiO₂ surface by lanthanum ion made it possible to enhance the photoactivity by retarding the recombination of photoexcited electron/hole pairs, in the result of the higher photoactivity in the stronger PL intensity.     

Novel synthesis of high-surface-area ordered mesoporous TiO2 with anatase framework for photocatalytic applications

Ordered mesoporous TiO₂ materials with an anatase frameworks have been synthesized by using a cationic surfactant cetyltrimethylammonium bromide (C₁₆TMABr) as a structure-directing agent and soluble peroxytitanates as Ti precursor through a self-assembly between the positive charged surfactant S⁺ and the negatively charged inorganic framework I^? (S⁺I^? type). The low-angle X-ray diffraction (XRD) pattern of the as-prepared mesoporous TiO₂ materials indicates a hexagonal mesostructure. XRD and transmission electron microscopy results and nitrogen adsorption–desorption isotherms measurements indicate that the calcined mesoporous TiO₂ possesses an anatase crystalline framework having a maximum pore size of 6.9 nm and a maximum Brunauer–Emmett–Teller specific surface area of 284 m² g^?1. This ordered mesoporous anatase TiO₂ also demonstrates a high photocatalytic activity for degradation of methylene blue under ultraviolet irradiation.     

The effect of Pt nanoparticles distribution on the removal of cyanide by TiO2 coated Al-MCM-41 in blue light exposure

With an aim to enhance the photocatalytic activity, Pt loaded TiO₂–Al-MCM-41 catalysts with high surface area were synthesized by a multistep route. The waste of the rice processing, rice husk (RH), was used as the precursor for the extraction of silica. The diffuse reflectance and photoluminescence spectroscopy revealed the extension of the absorption edge in the visible region and exciton trapping nature of the dispersed platinum. The structural analysis was carried out by XRD, whereas X-ray photoelectron spectroscopy identified the chemical states of the components of the synthesized powders. The BET surface area measurements revealed the reduction in the surface area and pore volume with the increasing platinum loading. TEM micrographs showed the uniform distribution of TiO₂ and Pt nanoparticles at the surface of Al-MCM-41. The photocatalytic efficiency of the synthesized powders as photocatalysts was obtained for the removal of 100 ppm CN⁻ from aqueous solution in fluorescent blue light exposure. Compared to unsupported TiO₂, the Pt-loaded catalysts exhibited substantially high activity for the removal of CN⁻. A plausible mechanism for the removal of cyanide ions was proposed. The catalysts showed excellent stability and reproducibility in the successive use.     

The effect of copper content on the reactivity of Cu/Co6Al2 solids in the catalytic steam reforming of methane reaction

The steam reforming of methane over Cu/Co₆Al₂ mixed oxides with different copper contents was studied. The Co₆Al₂ support was prepared via the hydrotalcite route. It was thermally stabilized at 500 °C, impregnated with 5 wt.%, 15 wt.% or 25 wt.% copper using copper (II) nitrate Cu(NO₃)₂·3H₂O precursor and then calcined again at 500 °C under an air flow. The impregnation of copper enhanced significantly the reactivity of the solids in the considered reaction. The 5Cu/Co₆Al₂ solid was the most reactive one, with a methane conversion of 96% at 650 °C. The selectivities of H₂ and CO₂ were also better for the catalyst containing 5 wt.% copper compared to higher copper loadings. The decrease in the catalytic reactivity with increasing the copper content was attributed to the formation of agglomerated and less reactive CuO species, which were detected by XRD and TPR analyses.