A new phosphor with flower-like structure and luminescent properties of Sr<Subscript>2</Subscript>MgSi<Subscript>2</Subscript>O<Subscript>7</Subscript>: Eu<Superscript>2+</Superscript>, Dy<Superscript>3+</Superscript> long afterglow materials by sol–gel method

The flower-like phosphors of Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺ with high brightness and long afterglow were obtained by sol–gel method. X-ray diffraction pattern (XRD) shows that single-phased Sr₂MgSi₂O₇ phosphor is prepared by sol–gel method under 1250 °C. Scanning electron microscope (SEM) indicates that the phosphor consists of nano-sized whiskers which are detected for the first time in Eu²⁺ and Dy³⁺ co-doped long-lasting phosphorescence silicates. Furthermore, the investigation on the mechanism indicates that the internal structure and gas, liquid and solid phase effect play important roles in the formation of flower-like Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺ nanostructure. Finally, the optical properties of flower-like Sr₂MgSi₂O₇ nanostructure have been characterized by photoluminescence (PL) spectra.     

UV excited green luminescence of SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript>:Eu<Superscript>2+</Superscript>, Dy<Superscript>3+</Superscript> nanophosphor

Eu, Dy co-doped strontium aluminate nanophosphors were prepared by the combustion synthesis method. Their structure and morphology were investigated by X-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy. According to the XRD and the TEM analysis, the average crystallite size was found to be in the nanometer range. The phase structure of the prepared nanophosphor is consistent with a standard monoclinic phase with a space group P2₁. The prepared SrAl₂O₄:Eu²⁺, Dy³⁺ nanophosphor emitted green light with a peak at 510 nm showing blue shift, which is due to the reduction in the particle size. Two distinct peaks were observed in the ML intensity versus time curve. The two peaks in ML indicate the presence of charge transfer in an ML process.     

Enhancement of the photoluminescence and long afterglow properties of Ca<Subscript>2</Subscript>MgSi<Subscript>2</Subscript>O<Subscript>7</Subscript>:Eu<Superscript>2+</Superscript> phosphor by Dy<Superscript>3+</Superscript> co-doping

The Ca₂MgSi₂O₇:Eu²⁺ and Ca₂MgSi₂O₇:Eu²⁺, Dy³⁺ long afterglow phosphors were synthesized under a weak reducing atmosphere by the traditional high temperature solid state reaction method. The synthesized phosphors were characterized by powder X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX) techniques. The luminescence properties were investigated using thermoluminescence (TL), photoluminescence (PL), long afterglow, mechanoluminescence (ML), and ML spectra techniques. The crystal structure of sintered phosphors was an akermanite type structure, which belongs to the tetragonal crystallography. TL properties of these phosphors were investigated, and the results were also compared. Under the ultraviolet excitation, the emission spectra of both prepared phosphors were composed of a broad band peaking at 535 nm, belonging to the broad emission band. When the Ca₂MgSi₂O₇:Eu²⁺ phosphor is co-doped with Dy³⁺, the PL, afterglow and ML intensity is strongly enhanced. The decay graph indicates that both the sintered phosphors contain fast decay and slow decay process. The ML intensities of Ca₂MgSi₂O₇:Eu²⁺ and Ca₂MgSi₂O₇:Eu²⁺, Dy³⁺ phosphors were proportionally increased with the increase of impact velocity, which suggests that this phosphor can be used as sensors to detect the stress of an object.     

Photocatalysis enhancement of CaAl<Subscript>2</Subscript>O<Subscript>4</Subscript>:Eu<Superscript>2+</Superscript>, Nd<Superscript>3+</Superscript>@TiO<Subscript>2</Subscript> composite powders

CaAl₂O₄:Eu²⁺, Nd³⁺@TiO₂ composite powders were synthesized by a sol–gel method under mild conditions (i.e. low temperature and ambient pressure). The as-prepared powders were characterized by transmission electron microscopy (TEM) and analyzed by X-ray diffraction (XRD). The photocatalytic behavior of the TiO₂-base surfaces was evaluated by the degradation of nitrogen monoxide gas. It suggested that CaAl₂O₄:Eu²⁺, Nd³⁺@TiO₂ composite powders were composed of anatase titania and that CaAl₂O₄:Eu²⁺, Nd³⁺. TiO₂ particles were deposited on the surface of CaAl₂O₄:Eu²⁺, Nd³⁺ to form uniform film. CaAl₂O₄:Eu²⁺, Nd³⁺@TiO₂ composite powders exhibited higher photocatalytic activity compared with pure TiO₂ under visible light. And the result also clearly indicated that the long afterglow phosphor absorbed and stored lights for the TiO₂ to remain photocatalytic activity in the dark.     

Effects of boric acid on structural and luminescent properties of BaAl<Subscript>2</Subscript>O<Subscript>4</Subscript>:(Eu<Superscript>2+</Superscript>, Dy<Superscript>3+</Superscript>) phosphors

Eu²⁺/Dy³⁺-codoped BaAl₂O₄ phosphors were prepared by conventional solid-state reaction with boric acid flux. The effects of boric acid on structural and luminescent properties of BaAl₂O₄:(Eu²⁺, Dy³⁺) were investigated. The crystallinity of BaAl₂O₄ improved with increasing amount of H₃BO₃. Incorporation of Eu²⁺ and Dy³⁺ ions into effective lattice sites was promoted by H₃BO₃ addition. As a result, Eu²⁺ emission in BaAl₂O₄ was greatly enhanced by H₃BO₃, and the duration of persistent luminescence increased with the amount of H₃BO₃. However, the decay lifetime of persistent luminescence was not strongly influenced by the amount of H₃BO₃.     

Eu<Superscript>3+</Superscript>-doped LaPO<Subscript>4</Subscript> and LaAlO<Subscript>3</Subscript> nanosystems and their luminescence properties

Eu³⁺ ion-doped LaPO₄ nanowires or nanorods have been successfully synthesized by a simple hydrothermal method. The influence of varying the hydrothermal and subsequent sintering conditions on the morphology and structure of the LaPO₄ host has been investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). For comparison, the Eu³⁺ ions were also doped into monoclinic monazite LaPO₄ nanoparticles and perovskite LaAlO₃ nanoparticles. The relative intensities of the emission lines of the LaPO₄:Eu³⁺ nanosystems were essentially independent of their shape. The optimal doping concentrations in the monoclinic LaPO₄ and perovskite LaAlO₃ nanosystems were determined to be about 5.0 and 3.5 mol%, respectively. Under appropriate UV-radiation, the red light emitted from LaAlO₃:Eu³⁺ (3.5 mol%) was brighter than that from LaPO₄:Eu³⁺ (5.0 mol%) nanomaterial, resulting from differences in their spin-orbit couplings and covalence, which indicates that the nanoscale LaAlO₃ is a promising host material for rare earth ions. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users. Supported by the National Natural Science Foundation of China (Grant Nos. 20873039 & 90606001), Hunan Provincial Natural Science Foundation (No. 07jj4002), and the Students Innovation Training Fund of Hunan University     

Thermochemical synthesis of luminescent materials in the Y<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZnO system doped with Eu<Superscript>3+</Superscript> ions

Powders were synthesized in the yttrium oxide + zinc oxide system doped with europium oxide by the method of redox combustion of a mixture of yttrium, zinc, and europium nitrates in the presence of saccharose (fuel). The structure and the physicochemical and luminescent properties of the particles being formed and of a ceramic on their basis were examined.     

Eu<Superscript>3+</Superscript>-fluorescence properties in nano-crystallized SnO<Subscript>2</Subscript>-SiO<Subscript>2</Subscript> glass-ceramics

Fluorescence and spectral hole burning properties of Eu³⁺ ions were studied in nanocrystals-precipitated SnO₂-SiO₂ glasses. The glasses were prepared to contain various amount of Eu₂O₃ using the sol-gel method, in which SnO₂ nanocrystals were precipitated by heating in air. In the glasses containing Eu₂O₃ less than 1%, the Eu³⁺ ions were preferentially doped in the SnO₂ nanocrystals and their fluorescence intensities were enhanced by the energy transfer due to the recombination of electrons and holes excited in SnO₂ crystals. The SnO₂ nanocrystals-precipitated glasses exhibited the persistent spectral holes with the depth of ∼25% of the total fluorescence intensities of the Eu³⁺ ions. With the increasing Eu₂O₃ concentration, the amount of SnO₂ nanocrystals decreased and the Sn⁴⁺ ions formed the random glass structure together with the silica network. This structure change induced the fluorescence intensities and the hole depth to decrease.     

Specific heat on Sr<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>7</Subscript> and Sr<Subscript>2</Subscript>Ta<Subscript>2</Subscript>O<Subscript>7</Subscript>

Summary Specific heats on the single crystals of Sr₂Nb₂O₇, Sr₂Ta₂O₇ and (Sr_1-xBa_x)₂Nb₂O₇ were measured in a wide temperature range of 2-600 K. Heat anomalies of a λ-type were observed at the incommensurate phase transition of T_INC (=495 K) on Sr₂Nb₂O₇ and at the super-lattice phase transition of T_SL (=443 K) on Sr₂Ta₂O₇; the transition enthalpies and the transition entropies were estimated. Furthermore, a small heat anomaly was observed at the low temperature ferroelectric phase transition of T_LOW (=95 K) on Sr₂Nb₂O₇. The transition temperature T_LOW decreases with increasing Ba content x and it vanishes for samples of x>2%.     

Synthesis and characterization of Eu<Superscript>3+</Superscript> doped Lu<Subscript>2</Subscript>O<Subscript>3</Subscript> nanophosphor using a solution-combustion method

Fine Eu³⁺-doped lutetium oxide (Lu₂O₃:Eu³⁺) nanophosphor were synthesized using a low-temperature solution-combustion method in a methyl-alcohol solution. The characteristics of the nanophosphors synthesized at various sintering temperatures with different Eu³⁺ concentrations were analyzed to determine the optimum synthesis conditions. Thermogravimetry/differential thermal analysis showed that Lu₂O₃:Eu³⁺ crystallizes completely when the dry powder is sintered at 500 °C. The Lu₂O₃:Eu³⁺ crystals had a cubic structure and monoclinic phase. The peak position of the luminescence spectrum did not differ with the concentration of Eu or the sintering temperature or atmosphere, whereas the luminescence intensity was strongly dependent on the concentration and sintering conditions.     

Incorporation of Mg<Superscript>2+</Superscript>, Sr<Superscript>2+</Superscript>, Ba<Superscript>2+</Superscript> and Zn<Superscript>2+</Superscript> into aragonite and comparison with calcite

We have investigated the presence of foreign ions into the bulk structure and the external surfaces of aragonite using periodic ab-initio methods. Four cations isovalent to Ca²⁺ were studied: Mg²⁺, Sr²⁺, Ba²⁺ and Zn²⁺. The calculations were performed at structures (bulk, surface) that contain four and eight CaCO₃ units. Our results, at the Hartree-Fock level, show that the incorporation of those ions into aragonite depends strongly on their size. Mg²⁺ and Zn²⁺, due to their smaller size, can substitute Ca²⁺ ions in the crystal lattice while the incorporation of Sr²⁺ and Ba²⁺ into aragonite is energetically less favoured. Examination of the [011], [110] and [001] surfaces of aragonite revealed that the surface incorporation reduces the energetic cost for the larger ions. These systems provide challenging examples for most shape analysis methods applied in Mathematical Chemistry.     

Near-infrared quantum cutting in Tb<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript>-doped Y<Subscript>2</Subscript>O<Subscript>3</Subscript> nanophosphors

Properties of the quantum-cutting phosphors are dependent on various factors such as dopant concentration, crystallinity, homogeneity, particle size and surface morphology. Effective control of the above parameters can enhance the quantum-cutting ability of the phosphor material. Nano-sized particles of Y₂O₃:Tb³⁺,Yb³⁺ were prepared with a solution-based co-precipitation method and subsequent calcination. Effective control of the reaction parameters and doping concentration helped to produce uniform nanostructures with high quantum-cutting efficiency up to 181.1 %. The energy transfer mechanism between Tb³⁺ and Yb³⁺ was studied by considering their spectroscopic properties and time-resolved spectroscopy. The high efficiency and small particle size of the quantum-cutting phosphor Y₂O₃:Tb³⁺,Yb³⁺ make it a suitable candidate for its application in solar cells.     

Kinetic aspects of the ion-exchange reactions of Cs<Superscript>+</Superscript>, Na<Superscript>+</Superscript>, Sr<Superscript>2+</Superscript>and Eu<Superscript>2+</Superscript> ions on the H<Superscript>+</Superscript> form of chromium hexacyanoferrate(II)

Summary This paper reports the radiochemical study of the ion-exchange of Cs⁺, Na⁺, Sr²⁺ and Eu³⁺ ions with H⁺ by chromium hexacyanoferrate(II) which was prepared in a granular form using a gel method. The slow steps which determine the rate of exchange of these ions are directly proportional to the particle diameter and this is confirmed from the linearity test of Bt vs. t plots at different particle diameters. Boyed’s equation and Reichenberg’s tables were used for evaluating all the kinetic parameters. The results reveal that the effective particle radii are unchanged for both chromium hexacyanoferrate(II) dried at 60 and 120 °C. The obtained data were analyzed using McKay plots and Arrhenius equation and the kinetic and thermodynamic parameters, e.g., effective diffusion coefficient, activation energies and entropies of activation have been evaluated. The mobility of these ions inside the particles of chromium hexacyanoferrate(II) decrease in the order of Eu³⁺>Sr²⁺>Na⁺⊃Cs⁺.     

Distribution of luminescence excitation energy between Eu<Superscript>3+</Superscript> and Tb<Superscript>3+</Superscript> ions fixed in a perfluorosulfonic membrane

Ion-exchange modification of MF-4SK perfluorosulfonic membranes with Eu³⁺ and Tb³⁺ cations was realized. The state of cations in the membrane was studied by X-ray photoelectron spectroscopy. Special features of the luminescence of the resulting systems point to preferential excitation energy transfer from europium to terbium.     

Hydrothermal synthesis of core-shell structured PS@GdPO<Subscript>4</Subscript>:Tb<Superscript>3+</Superscript>/Ce<Superscript>3+</Superscript> spherical particles and their luminescence properties

Non-aggregated spherical polystyrene (PS) particles were coated with GdPO₄:Tb³⁺/Ce³⁺ phosphor layers by a conventional hydrothermal synthesis using poly(vinylpyrrolidone) (PVP) as an additive without further annealing treatment. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), photoluminescence (PL), as well as luminescence decay experiments were used to characterise the resulting core-shell structured PS@GdPO₄:Tb³⁺/Ce³⁺ samples. The results of XRD indicated that the PS particles were successfully coated with the GdPO₄:Tb³⁺/Ce³⁺ phosphor layers, which could be further verified by the images of FESEM. Under ultraviolet excitation, the PS@GdPO₄:Tb³⁺/Ce³⁺ phosphors show Tb³⁺ characteristic emission, i.e. ⁵D₄-⁷F_J (J = {6, 5, 4, 3}) emission lines with green emission ⁵D₄-⁷F₅ (543 nm) as the most prominent group. The core-shell phosphors so obtained have potential applications in field emission display (FED) and plasma display panels (PDP).     

Gas-sensitivity properties of nanoscale Au-In<Subscript>2</Subscript>O<Subscript>3</Subscript> materials

A possibility was demonstrated of producing the chemical sensors based on Au-In₂O₃ obtained using a sol-gel technology. The sensors exhibit high sensitivity and selectivity toward CO. The differences in gas-sensitivity properties of In₂O₃ sensor with respect to CO and CH₄ at different ways of doping with Au(III) was examined. The effect of the gold nanoparticles size and the state of the indium oxide surface on the characteristics of Au-In₂O₃ and Au/In₂O₃ sensors at the detection of CO and CH₄ was examined.     

Influence of annealing temperature on material properties of red emitting ZnGa<Subscript>2</Subscript>O<Subscript>4</Subscript>: Cr<Superscript>3+</Superscript> nanostructures

Zinc gallate (ZnGa₂O₄) nanopowders doped with Cr³⁺ (1?mo%) were synthesized by the citric acid assisted sol–gel method. The influence of annealing temperature, structural, morphological, and optical properties of ZnGa₂O₄: Cr³⁺ (1?mol%) nanosized particles were investigated. The X-ray diffraction (XRD) spectra indicated that the nanoparticles are cubic in structure and the annealing temperature did not influence any c in structure. The average crystallite size of ZnGa₂O₄: Cr³⁺ nanoparticles were observed to increase from 11.85 to 30.88?nm as the annealing temperature increased from 600 to 1000?°C. The scanning electron microscopy (SEM) showed nearly spherical nanostructures that change in size with annealing temperature. The high resolution transmission electron microscope (HR-TEM) images show well resolved lattice fringes which is an indications of highly crystalline samples. Ultraviolet–visible (UV–Vis) measurement show decrease in reflectance in visible region and energy band gap was found to decrease with annealing temperature. The photoluminescence (PL) intensity was found to be maximum for sample annealed at high temperature (1000?°C) and least with sample annealed at low temperature (600?°C). An increase in annealing temperature leads significantly increment in PL intensity. The degree of crystallinity also increased with annealing temperature from XRD, SEM, and HR-TEM analysis. The photoluminescence lifetimes, particle size, and emission spectra are comparable with reports on bioimaging applications.

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A comparative study of Ir/Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>, Pt/Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>, and Ru/Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts in selective hydrogenation of crotonaldehyde

Catalytic performance of gallia-supported iridium catalysts in the reaction of selective hydrogenation of crotonaldehyde in the gas phase was studied and compared to that of platinum and ruthenium catalysts. The best catalytic properties in terms of the selectivity to crotyl alcohol are shown by 5 wt % Pt/α-Ga₂O₃ and 5 wt % Ir/α-Ga₂O₃ catalysts prepared from nonchlorine precursors: Pt(acac)₂ and Ir(acac)₃, but for the 5 wt % Pt/α-Ga₂O₃ a very high selectivity of 75% at the high conversion (ca. 60%) is observed. A high selectivity of galia-supported iridium and platinum catalysts was explained by the surface reducibility of gallium oxide leading to covering (decoration) of platinum and iridium by gallium suboxides and the promoting effect of gallium.