Ag-catalyzed synthesis of europium borate Eu(BO2)3 nanowires, growth mechanism and luminescent properties

Eu(BO₂)₃ nanowires with diameters of 10-20 nm were fabricated through direct sintering Eu(NO₃)₃·6H₂O and H₃BO₃ with Ag as catalyst. The result of X-ray diffraction (XRD) indicated that the nanowire was single-crystalline with body-centered monoclinic structure. Based on the fact that Ag nanoparticles attached to the tips and middles of nanowires, a vapor-liquid-solid (VLS) growth mechanism of the Eu(BO₂)₃ nanowires is proposed. Three well-defined stages have been clearly identified during the process: Ag-Eu-B-O cluster process, crystal nucleation, and axial growth. The photoluminescence characteristics under UV excitation were investigated. The dominated Eu³⁺ orange-red emission corresponding to the magnetic dipole transition ⁵D₀ → ⁷F₁ is centered at 591 nm, indicating that Eu³⁺ is located at high symmetry crystal field with inversion center.     

Synthesis and photoluminescence properties of SrLu2O4:Eu superfine phosphor

Superfine powder SrLu₂O₄:Eu³⁺ was synthesized with a precursor prepared by an EDTA - sol-gel method at relatively low temperature using metal nitrate and EDTA as starting materials. The heat decomposition mechanism of the precursor, formation process of SrLu₂O₄:Eu³⁺and the properties of the particles were investigated by thermo-gravimetric (TG) - differential thermal analysis (DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM) and photoluminescence (PL) analyses. The results show that pure SrLu₂O₄:Eu³⁺ superfine powder has been produced after the precursor was calcinated at 900 °C for 2 h and has an elliptical shape and an average diameter of 80-100 nm. Upon excitation with 250 nm light, all the SrLu₂O₄:Eu³⁺ powders show red and orange emissions due to the 4f-4f transitions of Eu³⁺ ions. The highest photoluminescence intensity at 610 nm was found at a content of about 6 mol% Eu³⁺. Splitting of the ⁵D₀-⁷F₁ emission transition revealed that the Eu³⁺ ions occupied two nonequivalent sites in the crystallite by substituting Lu³⁺ ions.     

Synthesis and photoluminescence properties of a new red emitting phosphor: Ca3(VO4)2:Eu; Mn

A new red emitting phosphor, Ca₃(VO₄)₂:Eu³⁺; Mn²⁺, was synthesized by a citric acid sol-gel combustion method and characterized by XRD, TEM and photoluminescence (PL) spectra. The red emission located at about 613 nm was ascribed to ⁵D₀-⁷F₂ transition of Eu³⁺. And the red luminescence intensity changed with annealing temperature and concentration of Eu³⁺. The effect of the co-doped Mn²⁺ was also investigated systematically.     

Hydrothermal synthesis and photoluminescence properties of nano-crystalline GdBO3:Eu phosphor

Nano-crystalline GdBO₃:Eu³⁺ was prepared by a hydrothermal method and the effects of some processing variables such as pH, temperature were investigated. The as-synthesized powders were spherical shaped agglomerates of nanoparticles. The luminescent properties were compared with samples synthesized by conventional solid-state reaction method. Both the photoluminescence intensity and chromaticity were improved and a red-shift in the CT band was observed for the hydrothermally synthesized samples. Possible mechanisms of phase formation were investigated and explanations for the changes in optical properties are proposed.     

M2Y8(SiO4)6O2: Tb (M = Ca, Sr) phosphors: Sol-gel synthesis from N-2-aminoethylic-3-aminopropyldiethoxysilane and different photoluminescence behavior

M₂Y₈(SiO₄)₆O₂: Tb³⁺ (M = Ca, Sr) phosphors have been synthesized with a new silicon source silane crosslinking reagent (N-2-aminoethylic-3-aminopropyldiethoxysilane [NH₂(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂], abbreviated as AEAPMMS) through the sol-gel process, both of which present the characteristic emission ⁵D₄ → ⁷F_J (J = 6, 5, 4, 3) of Tb³⁺ ions. It is interesting to be found that the high energy level blue emission (⁵D₃ → ⁷F_J (J = 6, 5, 4, 3) transition) still can be found in the emission spectrum of Ca₂Y₈(SiO₄)₆O₂: Tb³⁺ while it disappears in the emission spectrum of Sr₂Y₈(SiO₄)₆O₂: Tb³⁺ for the cross-relaxation-induced quenching.     

Gd2O3:Eu@mesoporous SiO2 bifunctional core-shell composites: Fluorescence label and drug release

A novel kind of core-shell nanocomposite Gd₂O₃:Eu³⁺@mesoporous SiO₂ was successfully fabricated, which consisted of a solvothermal synthesized Gd₂O₃:Eu³⁺ nanospheres core, a thin nonporous silica midterm layer and an ordered mesoporous silica shell. The XRD, SEM, TEM, FTIR, N₂ adsorption/desorption and PL spectra were employed to characterize the composites. The cytotoxicity of Gd₂O₃:Eu³⁺@mesoporous SiO₂ and Gd₂O₃:Eu³⁺ was assessed by the standard MTT assay. The composites had spherically monodisperse morphology and a narrow size distribution around 180 nm in diameter. Furthermore, they also demonstrated the strong photoluminescence of ⁵D₀-⁷F_J emissions. In addition, the composites exhibited good property of sustained drug release by using ibuprofen (IBU) as model drug in the drug delivery process. Therefore, the drug release process could be easily tracked and identified through photoluminescence. Overall, the present composites have potential significant biomedical application as ideal bifunctional materials.     

Synthesis and photoluminescence of nano-Y2O3:Eu phosphors

We report nano-Y₂O₃:Eu³⁺ phosphors with particle size of about 50 nm and relatively high photoluminescence (PL) intensity which is close to the standard for application. The influences of the dope amount, the surfactant and the precipitation pH on the PL intensity, the particle size and the dispersion have been studied. It has been found that 4% is the best Eu³⁺ molar concentration to get the highest PL intensity for both nano- and micro-Y₂O₃:Eu³⁺. The addition of butanol as a surfactant inhibits the grain growth and the agglomeration of particles efficiently by reducing the oxygen bridge bonds. As the pH rises, the PL intensity and the particle size increase due to the formation of oxygen bridge bonds.     

Synthesis and characterization of ZnO/SiO2 core/shell nanocomposites and hollow SiO2 nanostructures

In this paper, we prepared the ZnO nanoparticles by a simple hydrothermal method and fabricated the ZnO/SiO₂ core/shell nanostructures through a sol-gel chemistry process successfully. The hollow SiO₂ nanostructures were obtained by selective removal of the ZnO cores. The structure, morphology and composition of the products were determined by the techniques of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). The results indicated that the ZnO nanoparticles were sphere-like shape with the average size of 60 nm and belonged to hexagonal wurtzite crystal structure. With the coating of SiO₂, the vibration modes of Si-O-Si and Si-OH were found. Furthermore, the measurement results of optical properties showed that spectra of bare ZnO nanoparticles and ZnO/SiO₂ core/shell nanocomposites exhibited similar emission features, including a blue emission peak and an orange emission band.     

SrF2 hierarchical flowerlike structures: Solvothermal synthesis, formation mechanism, and optical properties

We present a solvothermal route to the synthesis of SrF₂ hierarchical flowerlike structures based on thermal decomposition of single source precursor (SSP) of strontium trifluoroacetate in benzylamine solvent. These flowerlike superstructures are actually composed of numerous aggregated nanoplates, and the growth process involves the initial formation of spherical nanoparticles and subsequent transformation into nanoplates, which aggregated together to form microdisks and finally flowerlike superstructures. The results demonstrate the important role of benzylamine in the formation of well-defined SrF₂ superstructures, not only providing size and shape control to form nanoplates but also contributing to the self-assembly behavior of nanoplates to build into flower-like superstructures. Additionally, the photoluminescence properties of the obtained SrF₂ superstructures are studied.     

Synthesis and photoluminescence properties of MgAl2O4:Mn hexagonal nanoplates

MgAl₂O₄:Mn²⁺ hexagonal nanoplates have been synthesized via a simple two-step method. The nanoplates have uniform hexagonal morphology with an average edge length of 1 μm and thickness of 30 nm. X-ray diffraction and various microscopic techniques indicate that MgAl₂O₄:Mn²⁺ nanoplates are single-crystal with multilayered morphology. The formation mechanism has also been discussed. Photoluminescence (PL) spectrum of the MgAl₂O₄:Mn²⁺ nanoplate shows a broad green emission band centered at 568 nm, which is assigned to the ⁴T₁ → ⁶A₁ transition of Mn²⁺ ion. The MgAl₂O₄:Mn²⁺ nanoplate is a promising candidate for efficient nanoscale optical material.     

Oriented organization of shape-controlled nanocrystalline TiO2

The self-assemble propensity of the controlled shape and size distribution titania nanoparticles makes the particles oriented organization to ordered structures without substrate by a hydrolysis-hydrothermal route. The procedure offers the possibility of a generalized approach to the production of patterned organization of single and complex oxide nanoparticles with size and morphology tunable.     

Crystal structures of KBa2Nb5O15 and LaK2Nb5O15 with the TTB-type structure

Single crystals of two niobates, KBa₂Nb₅O₁₅ and LaK₂Nb₅O₁₅, were synthesized by high-temperature reaction and the crystal structures were determined by single crystal X-ray diffraction data. Although the space groups for these compounds were different (the non-centrosymmetrical space group P4bm (#100) for KBa₂Nb₅O₁₅ and the centrosymmetrical one P4/mbm (#127) for LaK₂Nb₅O₁₅), both compounds had the same tetragonal tungsten bronze-type (hereafter TTB-type) structure. The lattice parameters and R-factors of KBa₂Nb₅O₁₅ (LaK₂Nb₅O₁₅) were a = 12.533(2) (12.563(2)) and c = 4.0074(9) (3.9179(9)) Å, and R₁ = 0.040 (0.047) and wR₂=0.131 (0.120), respectively. From the crystal structural analysis, it was clarified that distribution of two large cations was different from each other in the way that K and Ba atoms in KBa₂Nb₅O₁₅ were distributed statistically at two crystallographic sites and K and La atoms in LaK₂Nb₅O₁₅ were ordered.     

Alanine-assisted low-temperature combustion synthesis of nanocrystalline LiMn2O4 for lithium-ion batteries

Nanocrystalline LiMn₂O₄ powders have been synthesized by combustion process in a single step using a novel fuel, l-alanine. Thermogravimetric analysis and differential thermal analysis of the gel indicate a sharp combustion at a temperature as low as 149 °C. Quantitative phase analysis of X-ray diffraction data shows about 97% of phase purity in the as-synthesized powder, which on further calcination at 700 °C becomes single phase LiMn₂O₄. High Brunauer, Emmett, and Teller surface area values obtained for ash (53 m²/g) and calcined powder (23 m²/g) indicate the ultrafine nature of the powder. Average crystallite size is found to be ∼60-70 nm from X-ray diffraction analysis and transmission electron microscopy. Fourier transformed infra-red spectrum shows two strong bands at 615 and 511 cm⁻¹ originating from asymmetrical stretching of MnO₆ octahedra. A nominal composition of Li_0.88 Mn₂O₄ is calculated from the inductive coupled plasma analysis. From UV-vis spectroscopy, an optical band gap of 1.43 eV is estimated which is assigned to a transition between t_2g and e_g bands of Mn 3d. Electrochemical charge-discharge profiles show typical LiMn₂O₄ behavior with a specific capacity of 76 mAh/g.     

Y2O3:Eu microstructures: Hydrothermal synthesis and photoluminescence properties

Hexagonal microprisms of yttrium hydroxide (Y(OH)₃) with tuned diameter and height have been successfully prepared for the first time via a facile hydrothermal process using sodium citrate as the shape modifying agent. Y(OH)₃ microspheres with diameter of ca. 2.5 μm and microtubes with an average length about 13 μm, outer diameter about 3 μm and tube thickness about 800 nm were also obtained in current reaction systems. The possible formation mechanism for the Y(OH)₃ microstructures was briefly proposed. Y₂O₃:Eu³⁺ (5%) microstructures with similar morphologies was obtained after thermal treatment of the as-prepared Y(OH)₃:Eu³⁺ microstructures at 700 °C for 4 h. Results show that the relative emission intensity of the Y₂O₃:Eu³⁺ microprisms is about 8 times as those of the Y₂O₃:Eu³⁺ microtubes and microspheres under excitation of 259 nm ultraviolet light. The products were characterized by XRD, SEM, and EDS.     

Hydrothermal synthesis, characterization, photocatalytic activity and dye-sensitized solar cell performance of mesoporous anatase TiO2 nanopowders

Mesoporous anatase TiO₂ nanopowder was synthesized by hydrothermal method at 130 °C for 12 h. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected-area electron diffraction (SAED), HRTEM, and Brunauer-Emmett-Teller (BET) surface area. The as-synthesized sample with narrow pore size distribution had average pore diameter about 3-4 nm. The specific BET surface area of the as-synthesized sample was about 193 m²/g. Mesoporous anatase TiO₂ nanopowders (prepared by this study) showed higher photocatalytic activity than the nanorods TiO₂, nanofibers TiO₂ mesoporous TiO₂, and commercial TiO₂ nanoparticles (P-25, JRC-01, and JRC-03). The solar energy conversion efficiency (η) of the cell using the mesoporous anatase TiO₂ was about 6.30% with the short-circuit current density (Jsc) of 13.28 mA/cm², the open-circuit voltage (Voc) of 0.702 V and the fill factor (ff) of 0.676; while η of the cell using P-25 reached 5.82% with Jsc of 12.74 mA/cm², Voc of 0.704 V and ff of 0.649.     

Crystal structure and properties of the new complex vanadium oxide K2SrV3O9

The new complex vanadium oxide K₂SrV₃O₉ has been synthesized and investigated by means of X-ray powder diffraction (XPD), electron microscopy and magnetic susceptibility measurements. The oxide has an orthorhombic unit cell with lattice parameters a = 10.1922(2) Å, b = 5.4171(1) Å, c = 16.1425(3) Å, space group Pnma and Z = 4. The crystal structure of K₂SrV₃O₉ has been refined by Rietveld method using X-ray powder diffraction data. The structure contains infinite chains built by V⁴⁺O₅ square pyramids linked to each other via VO₄ tetrahedra. The chains form layers and potassium and strontium cations orderly occupy structural interstices between these layers. Electron diffraction as well as high resolution electron microscopy confirmed the structure solution. Magnetic susceptibility measurements revealed an antiferromagnetic interaction with J of the order of 100 K inside the chains and no long-range magnetic order above 2 K. The origin of the magnetic exchange is likely a result of super-exchange interaction through the two VO₄ tetrahedra linking the polyhedra with the magnetic V⁴⁺ cations.     

Luminescent properties of Gd2Ti2O7: Eu phosphor films prepared by sol-gel process

Gd₂Ti₂O₇: Eu³⁺ thin film phosphors were fabricated by a sol-gel process. X-ray diffraction (XRD), atomic force microscopy (AFM) and photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 800 °C and the crystallinity increased with the elevation of annealing temperatures. Uniform and crack free phosphor films were obtained, which mainly consisted of grains with an average size of 70 nm. The doped Eu³⁺ showed orange-red emission in crystalline Gd₂Ti₂O₇ phosphor films due to an energy transfer from Gd₂Ti₂O₇ host to them. Both the lifetimes and PL intensity of the Eu³⁺ increased with increasing the annealing temperature from 800 to 1000 °C, and the optimum concentrations for Eu³⁺ were determined to be 9 at.%. of Gd³⁺ in Gd₂Ti₂O₇ film host.     

Pr6O11 micro-spherical nano-assemblies: Microwave-assisted synthesis,characterization and optical properties

We report the synthesis of Pr₆O₁₁ microspheres self-assembled from ultra-small nanocrystals formed by the microwave irradiation of a solution of a salt of Pr in ethylene glycol (EG). The as-prepared product consists of microspheres measuring 200 to 500 nm in diameter and made of <5 nm nano-crystallites. The surface of these microspheres/nanocrystals is covered/capped with an organic layer of ethylene glycol as shown by TEM analysis and confirmed by IR spectroscopy measurements. The as-prepared product shows blue-green emission under excitation, which changes to orange-red when the product is annealed in air at 600 °C for 2 h. This change in luminescence behaviour can be attributed to presence of ethylene glycol layer in the as-prepared product. The samples were characterized by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), IR Spectroscopy (IR), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA).     

Aluminum doped zirconia nanopowders: Wet-chemical synthesis and structural analysis by Rietveld refinement

Alumina/zirconia nanopowders, with up to 20 mol% Al₂O₃, were prepared by wet-chemical synthesis technique, using controlled hydrolysis of alkoxides. The as-synthesized powders are amorphous, have very high specific surface area and the corresponding particle size smaller than 4 nm. Amorphous powders with 0, 10 and 20 mol% Al₂O₃ crystallize at 460, 692 and 749 °C, respectively, as a single-phase tetragonal zirconia, without any traces of alumina phases. Rietvled refinement of X-ray diffraction data, used for the detailed structural analysis of annealed nanopowders, showed that the high-temperature zirconia phase is stabilized due to the formation of ZrO₂/Al₂O₃ solid solutions. High solubility of alumina in the tetragonal zirconia (up to 28.6 at% Al³⁺) and stabilization of tetragonal zirconia solid solution up to high temperature (as high as 1150 °C) were also confirmed.     

Structural properties of Al2O3-La2O3 binary oxides prepared by sol-gel

The structural properties of La₂O₃ and Al₂O₃-La₂O₃ binary oxides prepared by sol-gel were studied by XRD, HRTEM and UV-vis. The binary oxides with high lanthana contents show an amorphous structure after calcination at 650 °C. At calcination temperatures higher than 1000 °C there is a phase transformation from the amorphous state to the crystalline LaAlO₃ with a perovskite structure. The structure of La₂O₃ is consistent with the hexagonal system; however, some crystalline microdomains with a monoclinic structure were detected by HRTEM. Islands of La₂O₃ and LaAl₁₁O₁₈ phases were detected at high lanthana concentration in the binary oxide. The modification in the coordination shell of the Al³⁺ cations due to the interaction with La³⁺ cations confirms the formation of phases with a perovskite structure and the presence of islands of the LaAl₁₁O₁₈ phase.