Observation directe par microscopie electronique a haute resolution de la transformation des hydroxycarbonates de terres rares (type B) en oxycarbonates (type II)

Type B rare earth hydroxycarbonate (LnOH)CO₃ is a lamellar hexagonal structure isomorphous to bastnaesite LnFCO₃. Type II oxycarbonate (LnO)₂CO₃ is another hexagonal lamellar structure built on an (LnO)ⁿ⁺_n complex cation of ternary symmetry. Lattice images were obtained for both compounds directly exhibiting the lamellar character. The thermal decomposition of the hydroxycarbonate into the oxycarbonate was followed in the electron microscope. The transition is topotactic and the crystallographic orientations were determined. The two compounds may have their triad axes and the $\text{[1}\text{1}\text{0]}$ (hydroxycarbonate) and [010] (oxycarbonate) axes in common, or the two thiad axes may be parallel and the lamellar structures may merge together. The oxycarbonate then appears in the form of bubbles in the hydroxycarbonate matrix, because of a slight deficiency (12 to 14) in the number of rare earth atom planes for the same distance along the triad axes for the oxycarbonate versus the hydroxycarbonate.     

Thermal decomposition of europium formate and oxalate

A complete and consistent scheme of the thermal decomposition of europium (III) formate and europium(III) oxalate was elucidated from the results of microthermogravimetry supplemented by DTA, evolved gas analysis, IR and X-ray powder diffraction examination of the products. In addition to the previously known oxycarbonate, namely Eu₂O₂CO₃ another oxycarbonate, Eu₂O(C0₃)₂, was shown to be an additional intermediate of the decomposition reaction. The sequence of the decomposition reaction of the formate was shown to be

     

水热法制备氧化钇空心纳米花及其吸附性能

采用水热法制备单分散、粒径均一的碱式碳酸钇(Y(OH)CO3)前驱体,经过高温煅烧处理得到氧化钇(Y_2O_3)空心纳米花。通过傅里叶转换红外分析(FT-IR),场发射扫描电子显微镜(FESEM),透射电子显微镜(TEM),X射线衍射(XRD),X射线能谱(XPS)以及N2吸-脱附等来表征样品,并研究了Y_2O_3空心纳米花吸附重铬酸钾(K2Cr2O7)的能力。实验结果表明:水热法制备的前驱体为Y(OH)CO3,经高温煅烧处理得到立方相Y_2O_3空心纳米花,尺寸约140 nm,比表面积为15 m2·g-1,讨论了Y_2O_3空心纳米花的形成机理。水热法制备的Y_2O_3空心纳米花对K2Cr2O7溶液的去除率可高达88.5%,吸附量为11.06 mg·g-1,约为Y_2O_3粉末的6倍。     

水热法制备氧化钇空心纳米花及其吸附性能

采用水热法制备单分散、粒径均一的碱式碳酸钇(Y(OH)CO₃)前驱体,经过高温煅烧处理得到氧化钇(Y₂O₃)空心纳米花。通过傅里叶转换红外分析(FT-IR),场发射扫描电子显微镜(FESEM),透射电子显微镜(TEM),X射线衍射(XRD),X射线能谱(XPS)以及N₂吸-脱附等来表征样品,并研究了Y₂O₃空心纳米花吸附重铬酸钾(K₂Cr₂O₇)的能力。实验结果表明:水热法制备的前驱体为Y(OH)CO₃,经高温煅烧处理得到立方相Y₂O₃空心纳米花,尺寸约140 nm,比表面积为15 m²·g^-1,讨论了Y₂O₃空心纳米花的形成机理。水热法制备的Y₂O₃空心纳米花对K₂Cr₂O₇溶液的去除率可高达88.5%,吸附量为11.06 mg·g^-1,约为Y₂O₃粉末的6倍。     

Growth and spectroscopic properties of Nd-doped Sr3Y2 (BO3)4 crystal

A new crystal of Nd³⁺:Sr₃Y₂ (BO₃)₄ with a dimension of Φ 15×30 mm³ was grown by the Czochralski method. The grown crystal was characterized using X-ray diffraction. The absorption and emission spectra of Nd³⁺:Sr₃Y₂ (BO₃)₄ were investigated. The absorption transition at 807 nm has an FWHM of 16 nm. The absorption and emission cross sections are 6.32×10⁻²⁰ cm² at 807 nm and 1.07×10⁻¹⁹ cm² at 1065 nm, respectively. The luminescence lifetime τ_f is 51.7 μs at room temperature.     

Synthesis and characterization of rare-earth doped SrBi2Nb2O9 phase in lithium borate based nanocrystallized glasses

Glass composites comprising of un-doped and samarium-doped SrBi₂Nb₂O₉ nanocrystallites are fabricated in the glass system 16.66SrO-16.66[(1−x)Bi₂O₃-xSm₂O₃]-16.66Nb₂O₅-50Li₂B₄O₇ (0?x?0.5, in mol%) via the melt quenching technique. The glassy nature of the as-quenched samples is established by differential thermal analyses. Transmission electron microscopic studies reveal the presence of about 15 nm sized spherical crystallites of the fluorite-like SrBi_1.9Sm_0.1Nb₂O₉ phase in the samples heat treated at 530 °C. The formation of layered perovskite-type un-doped and samarium-doped SrBi₂Nb₂O₉ nanocrystallites with an orthorhombic structure through the intermediate fluorite phase is confirmed by X-ray powder diffraction and micro-Raman spectroscopic studies. The influence of samarium doping on the lattice parameters, lattice distortions, and the Raman peak positions of SrBi₂Nb₂O₉ perovskite phase is clarified. The dielectric constants of the perovskite SrBi₂Nb₂O₉ and SrBi_1.9Sm_0.1Nb₂O₉ nanocrystals are relatively larger than those of the corresponding fluorite-like phase and the precursor glass.     

Synthesis and VUV-UV spectroscopic properties of rare earth borosilicate oxyapatite: RE5Si2BO13:Ln (RE=La, Gd, Y; Ln=Eu, Tb)

Three rare earth borosilicate oxyapatites, RE₅Si₂BO₁₃ (RE=La, Gd, Y), were synthesized via wet chemical method, of which RE₅Si₂BO₁₃ (RE=Gd, Y) were first reported in this work. In the three oxyapatites, [BO₄] and [SiO₄] share the [TO₄] tetrahedral oxyanion site, and RE³⁺ ions occupy all metal sites. The differential scanning calorimetry-thermo gravimetry measurements and high temperature powder X-ray diffraction pattern revealed a vitrification process within 300-1200 °C, which was due to the glass-forming nature of borosilicates. From the VUV excitation spectra of Eu³⁺ and Tb³⁺ in RE₅Si₂BO₁₃, the optical band gaps were found to be 6.31, 6.54 and 6.72 eV for RE₅Si₂BO₁₃ (RE=La, Gd, Y), respectively. The emission and excitation bands of Eu³⁺ and Tb³⁺ are discussed relating with their coordination environments. Among the three hosts, Y₅Si₂BO₁₃ would be the best for Eu³⁺ and Tb³⁺-doped phosphors.     

Effect of crystalline modification of the support on the reduction and catalytic properties of Cu/ZrO<Subscript>2</Subscript> catalysts in the steam reforming of bioethanol

A study was carried out on the steam reforming of bioethanol (15 vol.% ethanol in water) at 250–500 °C on copper catalysts supported on ZrO₂ of the monoclinic (Z) and yttrium-stabilized tetragonal crystalline modifications (YSZ). Copper nanoparticles in such catalysts have similar reactivity regardless of the copper content and crystalline modification of the support. Cu/YSZ is highly selective relative to CO₂, which may be related to enhanced mobility of oxygen in the support in the presence of Y₂O₃ stabilizing additive.     

CO2 在高分散 Ni/La2O3 催化剂上的甲烷化

 以 La2O3 为载体, 采用浸渍法制备了 10%Ni/La2O3 催化剂, 考察了该催化剂的 CO2 甲烷化反应性能. 结果表明, 在较低的温度 (350 oC) 和高空速 (约 30000 h–1) 下, 甲烷时空收率可大于 3000 g/(kg•h), 无论转化率高低, 甲烷选择性始终保持在 100%. X 射线衍射和 H2-程序升温还原等表征结果表明, CO2 在 Ni/La2O3 催化剂上的加氢机理可能与 Ni/γ-Al2O3 上不同, 并且 La2O2CO3 的形成有利于提高催化剂活性.     

Alpha-particle-induced luminescence of rare-earth-doped Y2O3 nanophosphors

The feasibility of utilizing Y₂O₃:Tb³⁺ and Y₂O₃:Eu³⁺ as radioluminescent nanophosphors under alpha-particle excitation is investigated. Materials synthesized by the urea homogeneous precipitation method were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). The XRD analysis of as-produced precipitates and nanophosphors fired at temperatures ranging from 950 to 1100 °C indicated the presence of highly crystalline cubic Y₂O₃ with crystallite sizes of ∼40 nm. SEM and TEM analysis revealed that particles with average diameters of ∼200 nm and comprised of ∼40 nm grains were obtained. High-resolution radioluminescence and photoluminescence spectra were used to investigate the unwanted radioluminescence saturation effects associated with the high ionization rate of alpha-particles. Additionally, the radioluminescence intensity as a function of rare-earth ion dopant concentration is investigated for these materials under alpha-particle excitation. The prospect for utilizing these materials as intermediate absorbers in indirect-conversion radioisotope batteries is discussed.     

Optical properties of (Y1−xTmx)3GaO6 and subsolidus phase relation of Y2O3-Ga2O3-Tm2O3

A serial of samples in Y₂O₃-Ga₂O₃-Tm₂O₃ pseudo-ternary system are prepared by solid-state chemical reaction method. The range of solid solution in (Y_1−xTm_x)₃GaO₆ is 0<x<0.384. Powder X-ray diffraction shows that the compounds crystallize in Gd₃GaO₆ (Cmc2₁)-type structure. The solid solubilities of Y_3+xGa_5−xO₁₂ (x=0-0.77) and Tm_3+xGa_5−xO₁₂ (x=0-0.62) are 37.5-47.11 at% Y₂O₃, and 37.5-45.26 at% Tm₂O₃, respectively. PL spectra of Tm-doped Y₃GaO₆ show that there is a sharp blue emission at ∼456 nm from the ¹D₂→³F₄ transition at room temperatures with two lifetimes (∼5 and ∼15 μs) and a narrow saturation range of PL intensity for the Tm³⁺ content from x=0.005 to 0.03. The sharp emission and long lifetime of (Y_1−xTm_x)₃GaO₆ indicate that Y₃GaO₆ is a potential phosphor and laser crystal host material.     

Intermediate steps in YBa2Cu3O7−x synthesis by sol-gel method: YBaCuO oxycarbonate

High T _c -superconducting powders of the Y-Ba-Cu-O system are prepared by a solution-polyacrylamide gel using citric acid as a complexing agent. This method provides an easy way to prepare reactive YBaCuO powders by sol-gel synthesis. However this synthesis involves intermediate phases formation which impedes the obtention of the pure phase at low temperature. An intermediate oxycarbonate phase forms between 800° and 850°C in flowing oxygen. From powder X-ray diffraction, thermal analysis and IR spectroscopy, it is concluded that the intermediate oxycarbonate has an average tetragonal structure—SG P4/mmm—similar to that of the parent oxide with a stoichiometry close to YBa₂Cu_2.95(CO₃)_0.35O_6.6. The carbonate group is located in the center of the basal CuO square. This compound has superconducting properties. A pure 123 phase is obtained when the xerogel precursor is annealed at 925°C in O₂ or at 800°C in Ar, then in O₂. The grain growth and microstructure development of YBaCuO have also been investigated and compared using two different powders, i.e. sol-gel route and commercial powder from Hoechst.     

Synthesis of nano-sized crystalline oxide ion conducting fluorite-type Y2O3-doped CeO2 using perovskite-like BaCe0.9Y0.1O2.95 (BCY) and study of CO2 capture properties of BCY

Formation of nano-sized Y₂O₃-doped CeO₂ (YCO) was observed in the chemical reaction between proton conducting Y₂O₃-doped BaCeO₃ (BCY) and CO₂ in the temperature range 700-1000 °C, which is generally prepared by wet-chemical methods that include sol-gel, hydrothermal, polymerization, combustion, and precipitation reactions. BCY can capture CO₂ of 0.13 g per ceramic gram at 700 °C, which is comparable to that of the well-known Li₂ZrO₃ (0.15 g per ceramic gram at 600 °C). Powder X-ray diffraction (PXRD), energy dispersive X-ray analysis (EDX), laser particle size analysis (LPSA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and ac impedance spectroscopy were employed to characterize the reaction product obtained from reaction between BCY and CO₂ and subsequent acid washing. PXRD study reveals presence of fluorite-like CeO₂ (a=5.410 (1) Å) structure and BaCO₃ in reaction products. TEM investigation of the acid washed product showed the formation of nano-sized material with particle sizes of about 50 nm. The electrical conductivity of acid washed product (YCO) in air was found to be about an order higher than the undoped CeO₂ reported in the literature.     

The solid state reaction between lanthanum oxide and strontium carbonate

The reaction between lanthanum oxide and strontium carbonate was studied non-isothermally between 350 and 1150 °C at different heating rates, intermediates and the final solid product were characterized by X-ray diffractometry (XRD). The reaction proceeds through formation of lanthanum oxycarbonate La₂O(CO₃)₂, lanthanum dioxycarbonate La₂O₂CO₃, and non-stoichiometric strontium lanthanum oxide La₂SrO_x (x = 4 + δ). La₄SrO₇ was found to be the final product which begins to form at ∼700 °C. Li⁺ doping enhances the formation of the final product as well as commencement of the reactions at lower temperatures.     

Enhanced quantum yield of yellow photoluminescence of Dy ions in nonlinear optical Ba2TiSi2O8 nanocrystals formed in glass

Transparent crystallized glasses consisting of nonlinear optical Ba₂TiSi₂O₈ nanocrystals (diameter: ∼100 nm) are prepared through the crystallization of 40BaO-20TiO₂-40SiO₂-0.5Dy₂O₃ glass (in the molar ratio), and photoluminescence quantum yields of Dy³⁺ ions in the visible region are evaluated directly by using a photoluminescence spectrometer with an integrating sphere. The incorporation of Dy³⁺ ions into Ba₂TiSi₂O₈ nanocrystals is confirmed from the X-ray diffraction analyses. The total quantum yields of the emissions at the bands of ⁴F_9/2→⁶H_15/2 (blue: 484 nm), ⁴F_9/2→⁶H_13/2 (yellow: 575 nm), and ⁴F_9/2→⁶H_11/2 (red: 669 nm) in the crystallized glasses are ∼15%, being about four times larger compared with the precursor glass. It is found that the intensity of yellow (575 nm) emissions and the branching ratio of the yellow (575 nm)/blue (484 nm) intensity ratio increase largely due to the crystallization. It is suggested from Judd-Ofelt analyses that the site symmetry of Dy³⁺ ions in the crystallized glasses is largely distorted, giving a large increase in the yellow emissions. It is proposed that Dy³⁺ ions substitute Ba²⁺ sites in Ba₂TiSi₂O₈ nanocrystals.     

Flame synthesized Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Tb<Superscript>3+</Superscript>–Yb<Superscript>3+</Superscript> phosphors as spectral convertors for solar cells

Near-infrared (NIR) quantum cutting phosphors serve as a potential material for fabricating photovoltaic spectral convertors. In many cases, quantum cutting phosphors are obtained via a wet chemical method coupled with a post-annealing treatment—a very costly process. In this report, we used continuous flame spray pyrolysis (FSP) for fabricating Y₂O₃:Tb³⁺–Yb³⁺ quantum-cutting phosphors without any post-treatment. Based on characterizations by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction, we found that as-synthesized Y₂O₃:Tb³⁺–Yb³⁺ phosphors exhibit hollow and shell-like micro-structures composed of highly crystalline and pure cubic-phase nanoparticles (< 50 nm). Photoluminescence studies of the phosphors revealed that NIR emissions appeared with the introduction of Yb to Y₂O₃:Tb³⁺. Phosphor size was successfully controlled by managing the concentration of the metal precursor solution for FSP. The Y₂O₃:Tb³⁺–Yb³⁺ phosphors were then embedded into transparent poly-ethylene-co-vinyl acetate (EVA) film to form a spectral convertor. The composite films of Y₂O₃:Tb³⁺–Yb³⁺ phosphors and poly-EVA were found to be highly transparent in the visible range (> 500 nm), making them suitable as spectral photovoltaic convertors.     

Solution combustion synthesized Y2O3 nanoparticles and influence of Dy doping on their microstructural,optical, and photoluminescence characteristics

Dy-doped Y₂O₃ nanoparticles were synthesized by solution combustion route with urea as fuel, and their microstructural features were analyzed by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). The XRD study confirms the formation of a pure cubic phase of Y₂O₃, with the maximum textural coefficient along the (2 2 2) plane for the Dy-doped samples. The lattice fringes in the HRTEM image and the bright spotty rings in the selected area electron diffraction (SAED) pattern reveal the highly crystalline nature of the nanoparticles. From the diffuse reflectance spectroscopy, using Kubelka-Monk theory, the direct bandgap energy is estimated to be 5.61 eV for the undoped Y₂O₃, which is found to decrease upon Dy³⁺ doping. The room-temperature excitation spectra of the nanoparticles recorded at 575 nm emission wavelength comprise several excitation bands corresponding to the f-f transitions of Dy³⁺ ions in the host lattice. The photoluminescence spectra of the nanoparticles excited at the wavelength of 350 nm comprise three visible emission peaks at 477 nm (blue), 573 nm (yellow), and 666 nm (red). It has been concluded that the 0.5 mol% Dy-doped Y₂O₃ nanoparticles are the potential candidate to be used for solid-state luminescent device applications.     

Thermal analysis of lanthanum hydroxide

Lanthanum oxide (La₂O₃) is of great interest as catalyst material. When La₂O₃ particles are prepared from lanthanum hydroxide (La(OH)₃) by thermal processes under air, various oxycarbonate phases are formed which are resistant to thermal hydroxylation. This phenomenon has not yet been extensively investigated, even though oxycarbonate phases at the particle surfaces cause a change in lanthanum oxide??s catalytic activity. The carbonate phases formed cannot be detected by means of XRD or REM-EDX investigations due to their detection limits. Thermal analysis, particularly TG-FT-IR, allows not only for the detection of the carbonate phases in La(OH)₃, but also for the tracking of the entire dehydration process from La(OH)₃ via LaOOH to La₂O₃ as well as the correct interpretation of mass changes during the thermal transformations. Pursuant to the investigations here carried out, it was determined that carbonate-free lanthanum hydroxide compounds can only be prepared and stored in a CO₂-free protective gas atmosphere (e.g., argon).     

UV-VUV-excited photoluminescence of RE-activated CaLaP3O10 (RE=Eu,Tb)

Monazite-type polyphosphate CaLaP₃O₁₀ was synthesized by solid-state reaction at 1000 °C and their photoluminescence of Eu³⁺ and Tb³⁺ in CaLaP₃O₁₀ under ultraviolet (UV) and vacuum-ultraviolet (VUV) excitation were evaluated for the first time. The emission spectra of CaLaP₃O₁₀:Eu³⁺showed that Eu³⁺ are in a site with inversion symmetry because the magnetic dipole transition ⁵D₀-⁷F₁ was the strongest both upon 254 and 147 nm excitation. Monitored at 621 nm the excitation spectra consisted of host absorption bands, charge transfer band of Eu-O and the intraconfiguration 4f⁶ transition of Eu³⁺. Green phosphor CaLaP₃O₁₀:Tb³⁺exhibited better color purity when excited by 147 nm than that excited by 254 nm. With monitored at 542 nm the host absorption bands of CaLaP₃O₁₀:Tb³⁺ were also observed. Besides the host absorption bands there were strong f-d and weak f-f transitions of Tb³⁺.     

Correlation of optical properties and temperature-induced irreversible phase transitions in europium-doped yttrium carbonate nanoparticles

Nanophase europium-doped yttrium carbonate precursors are subjected to heat treatments, ranging from 300 °C to 1100 °C for dwell times of 5 min, 30 min, and 180 min. XRD, TEM, FT-IR, fluorescence, fluorescence excitation, and fluorescence lifetime measurements are used to characterize the materials. Upon heating, the material transitions through several amorphous stages until it reaches the crystalline cubic Y₂O₃ phase. DSC measurements show an exothermic transition at 665.7 °C, indicating the formation of crystalline Y₂O₃. The grain size development is fitted by the relaxation equation and yields an activation energy of 50.3 kJ/mol. The amorphous phases are characterized by inhomogenously broadened optical spectra. Heating up to 700 °C leads to an increased fluorescence lifetime (from about 1 ms to 2.4 ms). As the material is heated to higher temperatures and completes the formation of the crystalline cubic Y₂O₃ phase, the optical spectra become narrower and the fluorescence lifetime decreases to about 1.2 ms.