Synthesis and photoluminescence of Eu-doped Y2Sn2O7 nanocrystals

A facile CTAB-assisted sol-gel route has been successfully established to synthesize Y₂Sn₂O₇ nanocrystals with pyrochlore structure. The route involves first the formation of CTAB-inorganics mesostructures as precursors and then their thermal decomposition to yield the final product. Well-crystallized and phase-pure Y₂Sn₂O₇ particles of ∼40 nm in size can be readily obtained at 600°C, a temperature much lower than that of the conventional solid-state method. Furthermore, photoluminescence characterization of the Y₂Sn₂O₇ nanocrystals doped with 5 mol% Eu³⁺ was carried out and the results show that the as-synthesized material display intense and prevailing emission at 589 nm belonging to the magnetic dipole transition.     

Raman scattering study of the geometrically frustrated pyrochlore Y2Ru2O7

Geometrically frustrated pyrochlore Y₂Ru₂O₇, which shows a spin-glass-like transition at T_G ∼ 80 K, were investigated by temperature-dependent Raman scattering. Three discernable phonons appear around 315, 410, and 510 cm⁻¹ without any abrupt change in the number of Raman active modes within the temperature range of 10–300 K. Fitting each phonon with Lorentz oscillators, we analyzed the effects of temperature on the phonon frequencies and the linewidths. The temperature-dependence of the mode near 510 cm⁻¹ shows abnormal behavior below T_G, while the other two phonons follow the usual thermal effect of lattice vibration. This behavior can be understood in terms of spin–phonon coupling. Considering the atomic modulations of each phonon mode, it is conjectured that the 510 cm⁻¹ phonon mode is isotropically coupled to the spin degree of freedom, while the other modes are not.     

Temperature-dependent Raman spectra of Bi2Sn2O7 ceramics

The Bi₂Sn₂O₇ pyrochlore is known to undergo a sequence of structural phase transitions with an increase in temperature. Raman spectroscopy was employed in the investigation of the temperature dependence of the active phonons in the Raman spectrum. We observed 19 broad modes at room temperature, reflecting the low symmetry of the α-phase of Bi₂Sn₂O₇. The modes were discussed in relation to the Raman spectra of other pyrochlore-based oxides. The temperature dependence of the phonons evidences the α → β structural phase transition observed near 127 °C.     

Structural change of layered perovskite La2Ti2O7 at high pressures

The perovskite-related layered structure of La₂Ti₂O₇ has been studied at pressures up to 30 GPa using synchrotron radiation powder X-ray diffraction (XRD) and Raman scattering. The XRD results indicate a pronounced anisotropy for the compressibility of the monoclinic unit cell. The ratio of the relative compressibilities along the [100], [010] and [001] directions is ∼1:3:5. The greatest compressibility is along the [001] direction, perpendicular to the interlayer. A pressure-induced phase transition occurs at 16.7 GPa. Both Raman and XRD measurements reveal that the pressure-induced phase transition is reversible. The high-pressure phase has a close structural relation to the low-pressure monoclinic phase and the phase transition may be due to the tilting of TiO₆ octahedra at high pressures.     

Visible and infrared luminescence properties of Er-doped Y2Ti2O7 nanocrystals

Er³⁺-doped Y₂Ti₂O₇ nanocrystals were fabricated by the sol-gel method. While the annealing temperature exceeds 757 °C, amorphous pyrochlore phase Er_xY_2−xTi₂O₇ transfers to well-crystallized nanocrystals, and the average crystal size increases from ∼70 to ∼180 nm under 800-1000 °C/1 h annealing. Er_xY_2−xTi₂O₇ nanocrystals absorbing 980 nm photons can produce the upconversion (526, 547, and 660 nm; ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2, and ⁴F_9/2→⁴I_15/2, respectively) and Stokes (1528 nm; ⁴I_13/2→⁴I_15/2) photoluminescence (PL). The infrared PL decay curve is single-exponential for Er³⁺ (5 mol%)-doped Y₂Ti₂O₇ nanocrystals but slightly nonexponential for Er³⁺ (10 mol%)-doped Y₂Ti₂O₇ nanocrystals. For 5 and 10 mol% doping concentrations, the mechanism of up-converted green light is the two-photon excited-state absorption. Much stronger intensity of red light relative to green light was observed for the sample with 10 mol% dopant. This phenomenon can be attributed to the reduced distance between Er³⁺-Er³⁺ ions, resulting in the enhancement of the energy-transfer upconversion and cross-relaxation mechanisms.     

Thermal properties of the pyrochlore, Y2Ti2O7

The thermal conductivity and heat capacity of high-purity single crystals of yttrium titanate, Y₂Ti₂O_7, have been determined over the temperature range 2 K?T?300 K. The experimental heat capacity is in very good agreement with an analysis based on three acoustic modes per unit cell (with the Debye characteristic temperature, θ_D, of ca. 970 K) and an assignment of the remaining 63 optic modes, as well as a correction for C_p−C_v. From the integrated heat capacity data, the enthalpy and entropy relative to absolute zero, are, respectively, H(T=298.15 K)−H₀=34.69 kJ mol⁻¹ and S(T=298.15 K)−S₀=211.2 J K⁻¹ mol⁻¹. The thermal conductivity shows a peak at ca. θ_D/50, characteristic of a highly purified crystal in which the phonon mean free path is about 10 μm in the defect/boundary low-temperature limit. The room-temperature thermal conductivity of Y₂Ti₂O₇ is 2.8 W m⁻¹ K⁻¹, close to the calculated theoretical thermal conductivity, κ_min, for fully coupled phonons at high temperatures.     

Preparation and Structure of Cerium Titanates Ce2TiO5, Ce2TiO7, and Ce4Ti9O24

Compounds Ce₂TiO₅, Ce₂Ti₂O₇, and Ce₄Ti₉O₂₄ were prepared by heating appropriate mixtures of solids containing Ce⁴⁺ and Ti³⁺ or Ti which were placed in a platinum-silica-ampoule combination at T = 1250°C (3d) under vacuum. The new compounds were characterized by powder patterns. We obtained Ce₂TiO₅ which is isotypic to La₂TiO₅ and crystallizes in the Y₂TiO₅-type (space group Pnma) with a = 10.877(6) Å, b = 3.893(1) Å, c = 11.389(8) Å, Z = 4. Ce₂Ti₂O₇ is isotypic to La₂Ti₂O₇ and crystallizes in the monoclinic Ca₂Nb₂O₇ type (space group P 2₁) with a = 7.776(6) Å, b = 5.515(4) Å, c = 12.999(6) Å, β = 98.36(5), Z = 4. The compound Ce₄Ti₉O₂₄ crystallizes orthorhombic with a = 14.082(4) Å, b = 35.419(8) Å, c = 14.516(4) Å, Z = 16. The new cerium titanate Ce₄Ti₉O₂₄ is isotypic to Nd₄Ti₉O₂₄ (space group Fddd (No. 70)) which represents a novel type of structure.     

Neutron diffraction studies of Gd2Zr2O7 pyrochlore

The structure of Gd₂Zr₂O₇ pyrochlore over the temperature range 4-300 K has been refined from powder neutron diffraction data. The sample was enriched in ¹⁶⁰Gd to avoid the high neutron absorption of naturally occurring Gd. The diffraction pattern showed well resolved superlattice reflections indicative of the pyrochlore structure and no evidence is found for anion-disorder from the structural refinements.     

O NMR studies of local structure and phase evolution for materials in the Y2Ti2O7-ZrTiO4 binary system

¹⁷O MAS NMR and XRD studies of precursor-derived Y_1.6Zr_0.4Ti₂O_7.2 and Y_1.2Zr_0.8Ti₂O_7.4 have been performed to investigate the development of local and long-range order in these materials as they evolve from a metastable amorphous state upon heating. Zirconium titanate (ZrTiO₄) was also investigated to help interpret the ¹⁷O NMR spectra of the ternary compositions. Consistent with earlier studies, crystallization was observed at 800 °C to form a fluorite structure and a small amount of rutile; weak broad reflections were also observed which were ascribed to the presence of small pyrochlore-like ordered domains or particles within the fluorite phase. As the temperature was increased further, the sizes of these domains grew along with the concentration of rutile. At the highest temperature studied (1300 °C), the reflections of the thermodynamic phases, pyrochlore and zirconium titanate (ZrTiO₄), dominated the XRD pattern. The ¹⁷O NMR spectra revealed a series of different peaks that were assigned to different 3- and 4-coordinate O local environments. The data were consistent with the formation of a metastable phase Y_2−xZr_xTi_2−yZr_yO_7+x with pyrochlore-like ordering but with Zr substitution on both cation sites of the pyrochlore structure. At low temperatures, doping on the A (Y³⁺) sites predominates (i.e., x>y), consistent with the fact that the pyrochlore develops out of a more disordered fluorite-like, phase. As the temperature is raised, the Zr doping on the A site decreases and the metastable phase at this temperature can now be written as Y_2−x′Zr_x′Ti_2−y′Zr_y′O_7+x′ (i.e., x′<y′); TiO₂ is also observed, consistent with this suggestion. At high temperatures, doping on the B site decreases and the resonances due to the stoichiometric pyrochlore yttrium titanate (Y₂Ti₂O₇) dominate the NMR spectra. Weaker ¹⁷O NMR resonances due zirconium titanate (ZrTiO₄) are also observed.     

Bi@Bi2Sn2O7/TiO2等离子体复合纤维的制备及增强的光催化产氢活性

以电纺TiO_2纳米纤维为基质,采用一步水热法合成了Bi@Bi_2Sn_2O_7/TiO_2等离子体复合纤维光催化剂。利用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、高分辨透射电镜(HRTEM)、紫外-可见漫反射(UV-Vis DRS)和光致发光光谱(PL)等分析测试手段对样品的物相、形貌和光电性能等进行表征。以三乙醇胺为电子给体,研究了Bi@Bi_2Sn_2O_7/TiO_2复合纤维光催化裂解水制氢的反应过程。结果表明:在水热过程中,Bi_2Sn_2O_7构筑在TiO_2纳米纤维表面形成p-n结的同时,部分Bi3+被葡萄糖还原成金属Bi沉积在Bi_2Sn_2O_7上。金属Bi的等离子体共振效应与p-n结的协同作用,有效提高了样品的光催化活性,产氢速率达到7.26 mmol·h~(-1)·g~(-1)。     

Synthesis and characterization of sodium titanates Na2Ti3O7 and Na2Ti6O13

Na₂Ti₃O₇ and Na₂Ti₆O₁₃ were synthesized by sol-gel method in order to obtain pure phases. Different heat-treatments were applied on powders and pellets of these materials. The effects were studied by XRD, dilatometry, TGA-DTA, SEM and electrochemical impedance spectroscopy. Pure Na₂Ti₃O₇ was obtained at 973 K. Sintering at 1373 K caused a partial decomposition into Na₂Ti₆O₁₃. The Na₂Ti₃O₇ powder sintered at 1273 K showed polygonal microstructure. Na₂Ti₃O₇ pellets sintered at 1323 K for 10 h exhibited large structures. This latter microstructure decreased the electrical conductivity of Na₂Ti₃O₇. Pure Na₂Ti₆O₁₃ was obtained at 873 K. Sintering at 1073 K caused a partial decomposition into TiO₂ (rutile). Na₂Ti₆O₁₃ pellets sintered at 1323 K for 10 h exhibited common shrinkage behavior. This shrinkage process increased the electrical conductivity of this material. The presence of TiO₂ resulted in a oxygen partial pressure dependence of the electrical conductivity.     

Solid solubilities of (La Nd,)2(Zr,Ti)2O7 phases deduced by neutron diffraction

Time-of-flight powder neutron diffraction has been performed on oxides with composition (La_1−xNd_x)₂Zr₂O₇ and Nd₂(Zr_1−xTi_x)₂O₇, where x=0, 0.2, 0.4,…1.0, in order to determine the solid solution behaviour across each series. Between La₂Zr₂O₇ and Nd₂Zr₂O₇, a cubic pyrochlore phase is observed (, Z=8). A linear decrease in the lattice parameter from 10.8047 to 10.6758 Å indicates complete miscibility of the two end-members. For the same series, the 48f oxygen x-parameter increases from 0.3313 to 0.3348, suggesting increased distortion of the 6 coordinate B sites and reduced distortion of the 8 coordinate A sites. There is limited solubility of Nd₂Ti₂O₇ in Nd₂Zr₂O₇. Exsolution of a monoclinic phase (P2₁, Z=8) rich in Nd₂Ti₂O₇ is observed at approximately x=0.56. The compositional range over which a solid solution exists is more extensive than that which has been previously reported. The solubility of Nd₂Zr₂O₇ in Nd₂Ti₂O₇ is very low.     

Formation and structural refinements of tunneled intergrowth phases in the Ga2O3-In2O3-SnO2-TiO2 system

Over 100 samples were prepared as (Ga,In)₄(Sn,Ti)_n−4O_2n−2, n=6, 7, and 9 by solid-state reaction at 1400 °C and characterized by X-ray diffraction. Nominally phase-pure beta-gallia-rutile intergrowths were observed in samples prepared with n=9 (0.17?x?0.35 and 0?y?0.4) as well as in a few samples prepared with n=6 and 7. Rietveld analysis of neutron time-of-flight powder diffraction data were conducted for three phase-pure samples. The n=6 phase Ga_3.24In_0.76Sn_1.6Ti_0.4O₁₀ is monoclinic, P2/m, with Z=2 and a=11.5934(3) Å, b=3.12529(9) Å, c=10.6549(3) Å, β=99.146(1)°. The n=7 phase Ga_3.24In_0.76Sn_2.4Ti_0.6O₁₂ is monoclinic, C2/m, with Z=2 and a=14.2644(1) Å, b=3.12751(2) Å, c=10.6251(8) Å, β=108.405(1)°. The n=9 phase Ga_3.16In_0.84Sn₄TiO₁₆ is monoclinic, C2/m, with Z=2 a=18.1754(2) Å, b=3.13388(3) Å, c=10.60671(9) Å, β=102.657(1)°. All of the structures are similar in that they possess distorted hexagonal tunnels parallel to the [010] vector.     

Hydrothermal synthesis and structure of the first tin(II) squarate Sn2O(C4O4)(H2O)—comparison with Sn2[Sn2O2F4]

A tin(II) squarate Sn₂O(C₄O₄)(H₂O) was synthesized by hydrothermal technique. It crystallizes in the monoclinic system, space group C2/m (no. 12) with lattice parameters a=12.7380(9) Å, b=7.9000(3) Å, c=8.3490(5) Å, β=121.975(3)°, V=712.69(7) Å³, Z=4. The crystal structure determined with an R=0.042 factor, consists of [(Sn₄O₁₀)(H₂O)₂] units connected from one another in the [101] and [010] directions via squarate groups to form layers separated by Sn(II) lone pairs. This compound presents the same remarkable structural arrangement as observed in the tin-oxo-fluoride Sn₂[Sn₂O₂F₄] inorganic compound with Sn(II) lone pairs E(1) and E(2) concentrated in large rectangular-shape tunnels running along [001] direction.     

Magnetic structure of pyrochlore-type Er2Ru2O7

Powder neutron diffraction measurements were carried out for the ruthenium pyrochlore oxide Er₂Ru₂O₇. The magnetic structure for this compound at 3.0 K has been solved using Rietveld analysis. The observed magnetic reflections suggest that the magnetic transitions are regarded as those to a long-range ordered state. It seems that the magnetic order of the Ru⁴⁺ and Er³⁺ magnetic moments occurs at 90 and 10 K, respectively.     

Synthesis and structural study of stoichiometric Bi2Ti2O7 pyrochlore

Bi₂Ti₂O₇ has been synthesized using a co-precipitation route from H₂O₂/NH_3(aq) solutions of titanium with aqueous bismuth nitrate. The stoichiometric material crystallizes into a pale yellow cubic pyrochlore phase. A powder X-ray diffraction study showed this crystallization to be very temperature sensitive, the pure phase can only be obtained within a few degrees of 470°C. Time-of-flight powder neutron diffraction studies of Bi₂Ti₂O₇ (Space group , a=10.37949(4) Å at ambient temperature, Z=8, R_p=3.95%, R_wp=4.75%) revealed positional disorder in the bismuth site and in the O′ oxide site both at ambient temperature and at 2 K.     

Ionic conductivity, structural and thermal properties of pure and Sr doped Y2Ti2O7 pyrochlores for SOFC

In the present study, SrO doped Yttrium titanate pyrochlore was synthesized using solid state reaction technique. The sintering characteristics, crystal structure, thermal and conductivity behavior of doped and undoped pyrochlores have been studied to find their suitability in solid oxide fuel cells (SOFC). The as-prepared samples were characterized using X-ray diffraction (XRD), Fourier-Transform-Infrared spectroscopy (FT-IR), thermal-gravimetric analysis (TGA) and ac conductivity up to 900 °C. The results are discussed in light of oxygen vacancy formation and structural disordering. Undoped and doped yttrium titanate with SrO (x = 0.1) exhibits single Y₂Ti₂O₇ phase with relative density of 94%. It was observed that further doping of SrO (x = 0.2–0.4) leads to formation of Y₂Ti₂O₇ phase along with SrTiO₃ phase. Excessive SrO (x = 0.4) results in increase in ionic conductivity to 1.50 × 10⁻¹ S cm⁻¹ whereas it impedes the densification process with relative density of 85%.     

Phase Relations at 1500°C in the Ternary System ZrO2–Gd2O3–TiO2

Phase relations at 1500°C in the ternary system ZrO₂–Gd₂O₃–TiO₂ have been determined by the powder X-ray diffraction of samples prepared by standard solid state reaction. A large area of this ternary oxide system centered on the Gd₂Ti₂O₇–Gd₂Zr₂O₇ join was shown to exhibit the pyrochlore and defect fluorite structures. The pyrochlore structure was observed for stoichiometries as far from the ideal M₄O₇ as M₄O_6.7 and M₄O_7.4, although the degree of disorder seemed much higher at these stoichiometries. On further deviation from the ideal M₄O₇ stoichiometry a smooth transition to fluorite average structure was observed for Zr-rich compositions. None of the other binary phases were observed to show significant extent of solid solution into the ternary region.     

Mild hydrothermal synthesis and ferrimagnetism of Pr3Fe5O12 and Nd3Fe5O12 garnets

Two pure light rare earth iron garnets Pr₃Fe₅O₁₂ and Nd₃Fe₅O₁₂ single crystals were synthesized under mild hydrothermal conditions and structurally characterized by single crystal and powder X-ray diffraction methods. Both compounds crystallize in cubic space group Ia3?d with lattice parameters a=12.670(2) Å for Pr₃Fe₅O₁₂ and a=12.633(2) Å for Nd₃Fe₅O₁₂, respectively. The synthesis of compounds was studied with regard to phase evolution and morphology development with hydrothermal conditions. We proposed the formation mechanisms and formulated a reasonable explanation for their growth habits. Ferrimagnetic Curie temperatures which have been inferred from thermo-magnetization curves were 580 K for Pr₃Fe₅O₁₂ and 565 K for Nd₃Fe₅O₁₂, and the transitions of long range order were also evidenced by differential scanning calorimetry method. The result of magnetic properties has shown that moments of the large radius Pr³⁺ and Nd³⁺ ions are parallelly coupled with net moments of iron ions.     

Composite Pd/Pr4O7/C catalysts: Synthesis, dispersity and properties

The catalysts prepared sequentiallyvia the interaction of C₃H₅PdC₅H₅ with the surface of evacuated Pr₄O₇/C and reduction with H₂ at 573 K, contain 20–30 Pd particles and Pr₄O₇ particles<20 . The catalysts obtained have two-order of magnitude higher specific activity in the CH₃OH synthesis than Pd/C.