The role of ligand coordination on the spectral features of Yb3+ ions in lead aluminum silicate glasses

The glasses of the composition (40 ? x)PbO–(5 + x)Al₂O₃–54SiO₂:1.0Yb₂O₃ (in mol%) with x ranging from 5 to 10 have been synthesized. The IR spectral studies of these glasses have indicated that there is a gradual transformation of Al³⁺ ions from tetrahedral to octahedral coordination with increase of Al₂O₃ content in the glass network. The optical absorption and luminescence spectra have exhibited bands originating from ²F_7/2 → ²F_5/2 and ²F_5/2 → ²F_7/2 transitions, respectively. From these spectra, the absorption and emission cross-sections and fluorescence lifetime of Yb³⁺ ions have been evaluated. Quantitative analysis of these data indicated a decreasing radiative trapping and increasing fluorescence lifetime of Yb³⁺ ions with increasing Al₂O₃ content. This may be explained by structural variations in the vicinity of Yb³⁺ ions due to variation in the concentration of Al₂O₃ in the glass network.     

Modeling of thermal and chemical non-equilibrium in a laser-induced aluminum plasma by means of a Collisional-Radiative model

A 0D numerical approach including a Collisional-Radiative model is elaborated in the purpose of describing the behavior of the nascent plasma resulting from the interaction between a 4 ns/65 mJ/532 nm Q-switched Nd:YAG laser pulse and an aluminum sample in vacuum. The heavy species considered are Al, Al⁺, Al²⁺ and Al³⁺ on their different excited states and free electrons. The translation temperatures of free electrons and heavy species are assumed different (T_e and T_A respectively). Numerous elementary processes are accounted for as electron impact induced excitation and ionization, elastic collisions, multiphoton ionization and inverse Bremsstrahlung. Atoms passing from the sample to gas phase are described by using classical vaporization theory so that the surface temperature is arbitrarily limited to values less than the critical point one at 6700 K. The laser flux density considered in the study is therefore moderate with a fluence lower than 7 J cm^? 2.This model puts forward the major influence of multiphoton ionization in the plasma formation, whereas inverse Bremsstrahlung turns out to be quasi negligible. The increase of electron temperature is mainly due to multiphoton ionization and T_e does not exceed 10,000 K. The electron induced collisions play an important role during the subsequent phase which corresponds to the relaxation of the excited states toward Boltzmann equilibrium. The electron density reaches its maximum during the laser pulse with a value ≈ 10²², 10²³ m^? 3 depending highly on the sample temperature. The ionization degree is of some percents in our conditions.     

[H4tren]3/2·(Al6F24)·3H2O,the most condensed fluoride in the Al(OH)3-tren-HFaq.-ethanol system

The most condensed crystalline fluoride that appears in the Al(OH)₃-tren-HF_aq.-ethanol system at 190 °C is found to be [H₄tren]_3/2·(Al₆F₂₄)·3H₂O. The structure is monoclinic, P2₁/c, with a = 21.939(1) Å, b = 6.7180(2) Å, c = 23.329(1) Å, β = 111.324(2)°. _∞(Al₆F₂₄) chains result from the connection of (Al₇F₃₀)⁹⁻ polyanions by opposite AlF₆ octahedra. Hydrogen bonds are established between the _∞(Al₆F₂₄) chains and ordered or disordered [H₄tren]⁴⁺ cations and water molecules.     

Electrothermal vaporization coupled with inductively coupled plasma array–detector mass spectrometry for the multielement analysis of Al2O3 ceramic powders

An electrothermal vaporization (ETV) system useful for the analysis of solutions and slurries has been coupled with a sector-field inductively coupled plasma mass spectrometer (ICP–MS) equipped with an array detector. The ability of this instrument to record the transient signals produced for a number of analytes in ETV–ICP–MS is demonstrated. Detection limits for Mn, Fe, Co, Ni, Cu, Zn and Ga are in the range of 4–60 pg μL^− 1 for aqueous solutions and in the low μg g^− 1 range for the analysis of 10 mg mL^− 1 slurries of Al₂O₃ powders. The dynamic ranges measured for Fe, Cu and Ga spanned 3–5 orders of magnitude when the detector was operated in the low-gain mode and appear to be limited by the ETV system. Trace amounts of Fe, Cu and Ga could be directly determined in Al₂O₃ powders at the 2–270 μg g^− 1 level without the use of thermochemical reagents. The results well agree with literature values for Fe and Cu, whereas deviations of 50% at the 90 μg g^− 1 level for Ga were found.     

Impact of Fe3+ on UV absorption of K2Al2B2O7 crystals

K₂Al₂B₂O₇ (KABO) is a new nonlinear optical crystal capable of laser harmonic generation in the UV range. However, abnormal UV absorption prevents its application in effectively generating UV light with wavelength shorter than 300 nm. The transmittance spectra of the grown crystals show distinct absorption bands at 216 nm and 264 nm. It is observed that the UV absorption is strongly correlated with iron impurity at a parts per million (ppm) level. Furthermore, electron paramagnetic resonance (EPR) spectra of the absorbing crystals show a strong signal at g = 2.00 position corresponding to a Fe³⁺ center. A new crystal growth method which reduces the iron content has been proposed and results show that the new KABO crystal is free from the Fe³⁺ UV absorptions.     

Electrochemical properties of Li symmetric solid-state cell with NASICON-type solid electrolyte and electrodes

All-solid-state phosphate symmetric cells using Li₃V₂(PO₄)₃ for both the positive and negative electrodes with the phosphate Li_1.5Al_0.5Ge_1.5(PO₄)₃ as the solid electrolyte were proposed. Amorphous Li_1.5Al_0.5Ge_1.5(PO₄)₃ was added into the electrode to increase the interface area between the active materials and the electrolyte. Any other phases were not formed at the electrode/electrolyte interface even after hot pressing at 600 °C. The discharge capacity was 92 mAh g^? 1 at 22 µA cm^? 2 at 80 °C, and 38 mAh g^? 1 at 25 °C, respectively. Symmetric cell configuration leads to simplify the fabrication process for all-solid-state batteries and will reduce manufacturing costs.     

Thermodynamic evaluation and optimization of the (NaCl + KCl + AlCl3) system

All available phase equilibrium and thermodynamic data for the (NaCl + KCl + AlCl₃) system were collected and critically evaluated. An optimization was performed to obtain the parameters of one set of model equations for each phase (solids, liquid, gas) in order to best reproduce all the data simultaneously. In this way the data are rendered self-consistent, discrepancies among the data are identified, and extrapolations and interpolations can be performed. For the molten phase the Modified Quasichemical Model for short-range ordering was used, with monomeric Al³⁺ ions (corresponding to AlCl₄⁻ complexes in earlier models) predominating in alkali-rich melts, and dimeric aluminum species (corresponding to Al₂Cl₇⁻ complexes in previous models) predominating in AlCl₃-rich melts. No ternary model parameters were required for the liquid phase; the binary parameters suffice. The models can be used with Gibbs free energy minimization software to calculate phase diagram sections, vapor pressures, and all thermodynamic properties at all compositions and over extended ranges of temperature and pressure.     

Study of CuZnMOx oxides (M = Al,Zr, Ce,CeZr) for the catalytic hydrogenation of CO2 into methanol

CuO–ZnO–Al₂O₃ catalysts were synthesized by two methods, sol–gel and co-precipitation syntheses. Al₂O₃ was then substituted with other supports, such as ZrO₂, CeO₂ and CeO₂–ZrO₂ in order to have a better understanding of the support's effect. These catalysts containing 30 wt% of Cu were then tested for CO₂ hydrogenation into methanol. The effect of reaction temperature and GHSV on the catalytic behaviour was also investigated. The best results were obtained with a 30 CuO–ZnO–ZrO₂ catalyst synthesized by co-precipitation and calcined at 400 °C. This catalyst presents a good CO₂ conversion rate (23%) with 33% of methanol selectivity, leading to a methanol productivity of 331 g_MeOH.kg_cata⁻¹·h⁻¹ at 280 °C under 50 bar and a GHSV of 10,000 h⁻¹.     

Flame atomic absorption spectrometry determination of trace amount of gold after separation and preconcentration onto ion-exchange polyethylenimine coated on Al2O3

The object of this work is to develop a simple and selective method for efficient extraction of Au(III) ions in aqueous solution using a new solid-phase extraction sorbent. Polyethylenimine (PEI) ion-exchange polymer was coated on alumina in the presence of NaNO₃. The method is based on sorption of Au³⁺ ions on 50 mg PEI/Al₂O₃. A solution of 0.5 M thiourea, then 1.0 M HCl effectively eluted the gold ion and then aspirated into flame atomic absorption spectroscopy (FAAS). The influence of flow rate of sample solution and eluent, the pH effect, eluent type and sorption capacity was investigated. The effects of various diverse ions for preconcentration and separation of the gold ion were investigated. Relative standard deviation of 4.0 μg mL⁻¹ of gold was 1.46% (n = 10). The detection limit was 26.2 ng L⁻¹ in original solution. The method has been applied successfully for the recovery of trace amount of Au(III) ions from water samples.     

Vacuum ultraviolet spectroscopic properties of rare earth (RE) (RE = Eu,Tb, Dy,Sm, Tm)-doped K2GdZr(PO4)3 phosphate

The luminescent characteristics of RE (RE³⁺ = Eu, Tb, Dy, Sm and Tm)-doped K₂GdZr(PO₄)₃ have been investigated. The band in the range of 130–157 nm in the VUV excitation spectra of these compounds is attributed to the host lattice or PO₄^3? group absorption and the band from 157 nm to 215 nm with the maximum at 188 nm is due to the O–Zr charge transfer transition. For Eu³⁺-doped sample, the relatively weak band of O^2?–Eu³⁺ charge transfer (CTB) at 222 nm is observed and for Tb³⁺-doped sample, the band at 223 nm is related to the 4f–5d spin-allowed transition of Tb³⁺. For Dy³⁺- and Sm³⁺-doped samples, the O^2?–Dy³⁺ and O^2?–Sm³⁺ CTBs have not been observed, probably due to the 2p electrons of oxygen tightly bound to the zirconium ion in the host lattice. In Tm³⁺-doped sample, the weak O^2?–Tm³⁺ CTB is located at 170 nm. It is observed that there is energy transfer between the host and the luminescent activators (e.g. Eu³⁺, Tb³⁺ and Sm³⁺) except for Tm³⁺.     

Electrochemical characterisation of MBaCo3ZnO7+δ (M = Y,Er, Tb) as SOFC cathode material with low thermal expansion coefficient

The electrochemical oxygen activation at high temperature was studied on a new class of oxygen-store material based on the system YBaCo₄O_7+δ. Three different porous layers made of YBaCo₃ZnO_7+δ, ErBaCo₃ZnO_7+δ and TbBaCo₃ZnO_7+δ were electrochemically tested as oxygen activation coatings and showed a very promising activity. The envisaged applications for these materials are principally as SOFC cathodes and as catalytic layer on oxygen membranes. The electrochemical performance followed the order Tb ? Y > Er at any tested temperature. Area specific resistance for the best performing material (TbBaCo₃ZnO_7+δ) ranges from 30 mΩ cm² at 850 °C to 0.46 Ω cm² at 650 °C. High temperature XRD showed that the thermal expansion coefficient (25–900 °C) in air of TbBaCo₃ZnO₇ is 9.45 × 10^?6 K^?1, which evidences the good thermochemical compatibility of this cobalt-rich electrocatalyst with YSZ/GDC electrolytes.     

Thermodynamic evaluation and optimization of the (NaF + AlF3 + CaF2 + BeF2 + Al2O3 + BeO) system

A complete critical evaluation of all available phase diagram and thermodynamic data has been performed for all condensed phases and relevant gaseous species of the (NaF + AlF₃ + CaF₂ + BeF₂ + Al₂O₃ + BeO) system, and optimized model parameters have been found. The (NaF + AlF₃ + CaF₂ + Al₂O₃) subsystem, which is the base electrolyte used for the electro-reduction of alumina in Hall–Héroult cells, has been critically evaluated in a previous article. The Modified Quasichemical Model in the Quadruplet Approximation for short-range ordering was used for the molten salt phase. The thermodynamic database developed is a first step towards a quantitative study of the beryllium mass balance in an electrolysis cell. In particular, the predominant Be-containing species in the gas phase evolved at the anode were identified; and, for a given beryllium content of the alumina, the beryllium content of the electrolytic bath at steady state was assessed under several approximations.     

Thermodynamic measurement of (Al2O3 + B2O3) system by double Knudsen cell mass spectrometry

Thermodynamic properties of B₂O₃ in the (Al₂O₃ + B₂O₃) binary system were investigated by vapor pressure measurement of B₂O₃ in equilibrium with (Al₂O₃ + B₂O₃) compounds or melts using double Knudsen cell mass spectrometry. The Gibbs free energy change of formation of Al₁₈B₄O₃₃ (9Al₂O₃·2B₂O₃) was estimated from the vapor pressure in equilibrium with a mixture of Al₁₈B₄O₃₃ and Al₂O₃ at 1573 K to 1673 K. And activities of B₂O₃ in the two-phase region Al₁₈B₄O₃₃ and B₂O₃-rich liquid, and (Al₂O₃ + B₂O₃) melts were obtained at 1373 K to 1423 K by vapor pressure measurements.     

A highly selective fluorescence turn-on detection of Al3+ and Ca2+ based on a coumarin-modified rhodamine derivative

A fluorescent chemosensor 1 was synthesized containing a coumarin moiety bound to rhodamine B hydrazide. Compound 1 displayed different fluorescence emission responses to Al³⁺ and Ca²⁺ ions with high quantum yields (0.64 and 0.15, respectively) and low detection limits (3.0 × 10^–8 and 9.4 × 10^–8 M, respectively). The possible binding modes of compound 1 with Al³⁺ and Ca²⁺ ion were calculated using a Job plot, HRMS, ¹H NMR spectroscopic titration and IR spectroscopy. Moreover, the calcium in 1-Ca²⁺ could be displaced by Al³⁺ ions, resulting in another ratiometric sensing signal output, which indicates that 1-Ca²⁺ could detect Al³⁺ ions in a ratiometric way. Bioimaging results also demonstrated that compound 1 could act as an intracellular Al³⁺ ion imaging sensor.     

Structural Properties of Ni/γ−Al2O3 and Cu/γ−Al2O3 Catalyst and its Application for Hydrogenation of Furfurylidene Acetone

Hydrogenation of furfurylidene acetone has been carried out using Ni/γ−Al₂O₃ and Cu/γ−Al₂O₃ catalyst in the presence of isopropanol in autoclave batch reactor. The hydrogenation using Cu/γ−Al₂O₃ at 120^oC for 6 h gives main formation of 1,5-bis-(furan-2-yl)-pentan-3-one. Reaction at higher temperature at 140^oC for 8 h using Ni/γ−Al₂O₃ leads to 1,5-bis-(furan-2-yl)-penta-1-en-3-one. The different selectivity of both catalysts is explained by physical properties including the surface area and distribution of metal loading.     

Microstructures and electrochemical hydrogen storage properties of novel Mg–Al–Ni amorphous composites

The amorphous Mg–Al–Ni composites were prepared by mechanical ball-milling of Mg₁₇Al₁₂ with x wt.% Ni (x = 0, 50, 100, 150, 200). The effects of Ni addition and ball-milling parameters on the electrochemical hydrogen storage properties and microstructures of the prepared composites have been investigated systematically. For the Mg₁₇Al₁₂ ball-milled without Ni powder, its particle size decreases but the crystal structure does not change even the ball-milling time extending to 120 h, and its discharge capacity is less than 15 mAh g^?1. The Ni addition is advantageous for the formation of Mg–Al–Ni amorphous structure and for the improvement of the electrochemical characteristics of the composites. With the Ni content x increasing, the composites exhibit higher degree of amorphorization. Moreover, the discharge capacity of the composite increases from 41.3 mAh g^?1 (x = 50) to 658.2 mAh g^?1 (x = 200) gradually, and the exchange current density I₀ increases from 67.1 mA g^?1 (x = 50) to 263.8 mA g^?1 (x = 200), which is consistent with the variation of high-rate dischargeability (HRD). The ball-milled Mg₁₇Al₁₂ + 200 wt.% Ni composite has the highest cycling discharge capacity in the first 50 cycles.     

Some aspects of metal-support strong interactions in Rh/Al2O3 catalyst under oxidising and reducing conditions

The aim of the Letter is to elucidate the nature of metal-support interaction in the 2 wt% Rh/Al₂O₃ catalyst obtained by annealing Rh–O–Al xerogel at 1113 K in air.XPS, HRTEM, and XRD results reveal that during the Rh–O–Al xerogel annealing in air, rhodium incorporates into forming alumina, which results mostly in Rh⁴⁺/δ-Al₂O₃ solid solution formation.However, in the course of the catalyst reduction at 773 with H₂ and at 823 K with CH₄ the Rh⁴⁺/δ-Al₂O₃ solid solution transforms into Rh–Al alloy. The islands of rhodium form on the surface of the Rh–Al alloy nanocrystallites if the reduction is slow enough.     

Improved luminescent behavior of YVO4:Eu3+ ceramic phosphors by Li contents

Crystalline phase and surface morphology of phosphors are important factors to determine luminescent characteristics. Li-doped YVO₄:Eu³⁺ ceramic samples were prepared by a solid state reaction method. The Li⁺ concentration was varied from 1 to 3 wt% to improve crystallinity and surface morphology of ceramics. Influence of Li doping on luminescent properties of YVO₄:Eu³⁺ ceramics has been investigated. Photoluminescence spectra have been measured at room temperature using a luminescence spectrometer and excitation by a broadband incoherent ultraviolet light source with an excitation wavelength of 325 nm. The emitted radiation was dominated by a red emission peak at 620 nm radiated from the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions. As Li⁺ ion content increases from 0 to 2 wt%, the photoluminescence (PL) brightness improved. The brightness of 2 wt% Li-doped YVO₄:Eu³⁺ ceramic was increased by a factor of 1.43 in comparison with that of YVO₄:Eu³⁺ ceramic. The enhanced luminescence resulted not only from the improved crystallinity but also from the enhanced surface roughness. The luminescent intensity and surface roughness exhibited similar behavior as a function of Li⁺ ion concentration.     

Photocatalytic reduction of cadmium over CuFeO2 synthesized by sol–gel

The Cd²⁺ photo-electrodeposition was successfully carried out in air-equilibrated aqueous CuFeO₂ suspension. The delafossite CuFeO₂ is p-type semiconductor characterized by a low optical gap, properly matched to the sun spectrum, and a long term chemical stability in neutral solution. It has been elaborated by the sol–gel technique where the specific surface area is increased via the surface/bulk ratio. The TG/DSC plots and IR spectra show that the solid phases are formed only at temperatures exceeding 400 and at 700 °C, the system is mixed phases. When fired at 950 °C under nitrogen flow, the delafossite has been identified (CuO + CuFe₂O₄ → CuFeO₂ + ½O₂). All the XRD lines index in a hexagonal unit cell with the lattice constants a = 284.2 and c = 169.4 pm. The photocurrent onset potential (+0.35 V_SCE) is close to the flat band potential (+0.23 V_SCE) determined from the capacitance measurement. CuFeO₂/Cd²⁺ solution is a self photo-driven system, the absorption of light promotes electrons into CuFeO₂–CB with a potential (?0.93 V_SCE) sufficient to reduce Cd²⁺. This occurs because of the dark Cd²⁺ adsorption on the surface powder. The system was optimized with respect to the following physical parameters: pH 6.8, Cd²⁺ (100 ppm) and a mass concentration C_m (1 mg catalyst/ml solution). The hetero-system CuFeO₂/TiO₂ has been also reported for a comparative purpose. Prolonged irradiation (>50 min) was accompanied by a pronounced decrease in the rate of Cd-deposition owing to the competitive water reduction. Indeed, the generated bi-functional CuFeO₂/Cd particles account for the low over-potential of hydrogen and favour its evolution in aqueous solution.     

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.