Synthesis,structure, and physicochemical properties of compounds Pb(B<Superscript>V</Superscript>UO<Subscript>6</Subscript>)<Subscript>2</Subscript> ⋅ <Emphasis Type="Italic">n</Emphasis>H<Subscript>2</Subscript>O (B<Superscript>V</Superscript> = P,As, V)

Compounds Pb(B^VUO₆)₂ nH₂O (B^V = P, As, V) were synthesized and studied by X-ray diffraction, IR spectroscopy, thermal analysis, and reaction calorimetry. The standard enthalpies and Gibbs energies of formation of the compounds at T = 298 K were determined, and processes involving these compounds were quantitatively characterized.Translated from Radiokhimiya, Vol. 46, No. 5, 2004, pp. 412–417.Original Russian Text Copyright © 2004 by Suleimanov, Chernorukov, Golubev.     

Synthesis,electronic state,and particle size stabilization of nanoparticulate [Co(OH)<Subscript>2</Subscript>(H<Subscript>3</Subscript>O)<Stack><Subscript>δ</Subscript><Superscript>+</Superscript></Stack>]<Superscript>δ+</Superscript>

We have synthesized nanoparticulate cobalt(II) hydroxide containing Co²⁺ in tetrahedral oxygen coordination (Co _Td ²⁺ ), atypical of such systems: nano- [Co(OH)₂(H₃O) _δ ⁺ ]^δ+. The (Co _Td ²⁺ ) coordination in the hydroxide is inferred from its electronic diffuse reflectance spectrum, which shows a multiplet of strong absorption bands at 14500, 15000, and 16000 cm^?1 (⁴ A ₂(F)-⁴ T ₁(P) transition). Nanoparticulate cobalt(II) hydroxide forms in a weakly acidic medium under essentially nonequilibrium conditions due to supersaturation (by three to four orders of magnitude) with the starting reagents (CoCl₂ and LiOH) at the instant of the formation of the poorly soluble phase Co(OH)₂. Presumably, colloidal particles of nanoparticulate cobalt(II) hydroxide in a weakly acidic aqueous medium have a positive surface charge, compensated by a counter-ion (Cl^?) layer: nano-[Co(OH)₂(H₃O) _δ ⁺ ]^δ+ · δCl^?. The XRD patterns of pastes (gels) containing this hydroxide show three broad-ened lines with d = 5.31 (2θ = 16.7°), 2.77 (2θ = 32.3°), and 2.32 Å (2θ = 38.8°). According to small-angle X-ray scattering data, nano-[Co(OH)₂(H₃O) _δ ⁺ ]^δ+ has a narrow particle size distribution (1.0–2.0 nm). Synthesis and storage conditions are identified which ensure stabilization of the electronic state and particle size of nano-[Co(OH)₂(H₃O) _δ ⁺ ]^δ+ for a long time.     

Stability of the LaCl<Stack><Subscript>4</Subscript><Superscript>−</Superscript></Stack> and LuCl<Stack><Subscript>4</Subscript><Superscript>−</Superscript></Stack> Ions Studied by Mass Spectrometry

The enthalpy stability of the LaCl ₄ ^? and LuCl ₄ ^? ions is assessed using high-temperature mass spectrometry. The enthalpy of Cl^? detachment is determined to be Δ_rH⁰(298.15 K) = 332 ± 10 kJ/mol for LaCl ₄ ^? and 359 ± 10 kJ/mol for LuCl ₄ ^? .     

Synthesis and characterization of the M<Superscript>II</Superscript>U<Subscript>3</Subscript>O<Subscript>10</Subscript> · 6H<Subscript>2</Subscript>O (M<Superscript>II</Superscript> = Ni,Zn) triuranates

We have developed a process for the synthesis of Ni(II) and Zn(II) triuranates with the general formula M^IIU₃O₁₀ · 6H₂O through reaction of schoepite, UO₃ · 2.25H₂O, with aqueous solutions of nickel and zinc nitrates under hydrothermal conditions. Using chemical analysis, X-ray diffraction, IR spectroscopy, and thermal analysis, we have determined the composition and structure of the triuranates and investigated their dehydration and thermal decomposition.     

Tunable luminescence and energy transfer properties in Ca<Subscript>2−x</Subscript>NaMg<Subscript>2</Subscript>V<Subscript>3</Subscript>O<Subscript>12</Subscript>:xEu<Superscript>3+</Superscript> phosphors

Novel broadband luminescence phosphors Ca_2?xNaMg₂V₃O₁₂:xEu³⁺ have been successfully prepared via the conventional high-temperature solid-state reaction. The effects of concentrations of doped Eu³⁺ and introducing Li⁺, K⁺ on the luminescent properties of phosphor were studied. X-ray diffraction, GSAS structural refinement and photoluminescence spectra were used to characterize the samples. The refinement data ensured where the doped Eu³⁺ ions occupied the lattice site in the host. Under 355 nm excitation, the emission peak of Ca₂NaMg₂V₃O₁₂:Eu³⁺ phosphors are located at 610 nm (red) ascribed to the electric dipole transition of Eu³⁺ from ⁵D₀ → ⁷F₂. In the range of 400–575 nm, Ca₂NaMg₂V₃O₁₂:Eu³⁺ phosphors have broad emission bands attributed to charge transfer of \({\text{VO}}_4^{3 - }\) group. Energy transfer mechanism, energy transfer efficiency and critical distance (R_c) of \({\text{VO}}_4^{3 - }\) → Eu³⁺ would be analyzed. The emitting color of Ca₂NaMg₂V₃O₁₂:Eu³⁺ could be tunable from blue-green to near white light.     

Probe Mössbauer Spectroscopy of BiNi<Subscript>0.96</Subscript><Superscript>57</Superscript>Fe<Subscript>0.04</Subscript>O<Subscript>3</Subscript>

This paper presents results of a ⁵⁷Fe probe Mössbauer spectroscopy study of the BiNi_0.96⁵⁷Fe_0.04O₃ nickelate. The spectra measured above its TN demonstrate that Fe³⁺ cations heterovalently substitute for Ni²⁺ nickel (←Fe³⁺), being stabilized on four sites of the nickel sublattice in the structure of BiNiO₃. Calculations in an ionic model with allowance for monopole and dipole contributions to the electric field gradient indicate that the parameters of electric hyperfine interactions between ⁵⁷Fe probe atom nuclei reflect the specifics of the local environment of the nickel in the structure of the unsubstituted BiNiO₃ nickelate. Below T^N, Mössbauer spectra transform into a complex Zeeman structure, which is analyzed in terms of first-order perturbation theory with allowance for electric quadrupole interactions as a small perturbation of the Zeeman levels of the ⁵⁷Fe hyperfine structure, as well as for specific features of the magnetic ordering of the Ni²⁺ cations in the nickelate studied.     

Structure,electrical, and optical properties of ZnO-substituted PbO for the Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript> co-doped Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–GeO<Subscript>2</Subscript>–Na<Subscript>2</Subscript>O glass system

Glasses of the 0.5Er³⁺/2.5Yb³⁺ co-doped (40Bi₂O₃–20GeO₂–(30 − x)PbO–xZnO–10Na₂O system where x = 0.0, 5, 10, 15, 20, 25, and 30 mol%) have been characterized by FT-IR spectroscopy measurements to obtain information about the influence of ZnO-substituted PbO on the local structure of the glass matrix. The density and the molar volume have been determined. The influences of the ZnO-substituted PbO on the structure of glasses have been discussed. The dc conductivity measured in the temperature range 475–700 K obeys Arrhenius law. The conductivity decreases while the activation energy for conduction increases with increase ZnO content. The optical transmittance and reflectance spectrum of the glasses have been recorded in the wavelength range 400–1100 nm. The values of the optical band gap E _opt for all types of electronic transitions and refractive index have been determined and discussed. The real and imaginary parts ε₁ and ε₂ of dielectric constant have been determined.     

Formation-decomposition equilibrium of the NpO<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack>·UO<Stack><Subscript>2</Subscript><Superscript>2+</Superscript></Stack> complex in chloride melts

The absorption spectra of the NpO ₂ ⁺ (5f ²) ion were examined in the region of the 3H ₅ ← ³ H ₄ magnetic dipole transition (1530–1760 nm) for series of melts with the UO ₂ ²⁺ concentration varied in the opposite directions: (1) NaCl-2CsCl eutectic melt with growing additions of the Cs₂UO₂Cl₄ complex salt and (2) Cs₂UO₂Cl₄ melt with growing additions of the NaCl-2CsCl mixture. Measurements of the integrated intensities of the bands belonging to the NpO ₂ ⁺ ·UO ₂ ²⁺ complex and unbound NpO ₂ ⁺ throughout the UO ₂ ²⁺ concentration range examined (up to 4.4 M in neat Cs₂UO₂Cl₄ melt) and processing of the data obtained in terms of the mass action law showed that the formation-decomposition reaction of the cation-cation complex can be described adequately only using the equation of reaction in the form NpO₂Cl ₄ ^3? + UO₂Cl ₄ ^2? ? {Cl₄ONpO?UO₂Cl₃}^4? = Cl^? (with the equilibrium constant of 1.3±0.1). Thus, the formation of the cationcation complex should be treated as replacement of chloride ion in the equatorial plane of uranyl(VI) by neptunyl(V), rather than as simple addition of UO ₂ ²⁺ to NpO ₂ ⁺ . The reverse reaction, decomposition of the cation-cation complex, consists essentially in replacement of neptunyl(V) by chloride ion.     

Estimating the effect of C<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> and C<Stack><Subscript>3</Subscript><Superscript>+</Superscript></Stack> radicals and neutral clusters on the fullerene formation

The mass spectrum of the products of arc discharge in helium between graphite electrodes has been studied for various values of the gas flow rate. As the gas flow rate increases, the intensity of C₆₀^±, C₇₀^±, C₈₄^± and C₉₀^± fullerene peaks increases and that of the C₂⁻ and C₃⁺ cluster radicals decreases, but the total decay in radicals amounts to only 21% of the total growth of fullerenes. From this it follows that a contribution to the formation of fullerenes from the neutral clusters (which are taken into account for the first time) significantly exceeds the contribution due to small radical species.     

Synthesis and photoluminescence characterization of Ce<Superscript>3 + </Superscript> and Dy<Superscript>3 + </Superscript> activated ALa(WO<Subscript>4</Subscript>)<Subscript>2</Subscript>(A = Na and Li) novel phosphors

In this paper, we report the synthesis of Ce^3 + and Dy^3 + activated alkali lanthanide tungstates, ALa(WO₄)₂(where A = Na and Li), prepared by solid state reaction method. The prepared phosphors were characterized by X-ray diffraction and photoluminescence techniques. The NaLa(WO₄)₂:Dy^3 + and LiLa(WO₄)₂:Dy^3 + phosphors show two emission peaks at around 574 and 486 nm (λ_exc = 354 nm). NaLa(WO₄)₂:Ce^3 + and LiLa(WO₄)₂:Ce^3 + show two emission peaks at around 378 and 425 nm (λ_exc = 350 nm). Excitation wavelengths of Ce^3 + and Dy^3 + activated alkali lanthanide tungstates are in near UV region i.e. Hg free excitation. These characterizations of phosphors are applicable for solid state lighting. Accordingly, Ce^3 + and Dy^3 + activated NaLa(WO₄)₂ and LiLa(WO₄)₂ may be the promising materials for solid state lighting applications.     

Y<Subscript>2</Subscript>O<Subscript>2</Subscript>S:Er<Superscript>3+</Superscript>,Ce<Superscript>3+</Superscript>—A new “invisible” IR phosphor

Ce³⁺ doping of Y₂O₂S:Er³⁺ can be used to suppress the visible anti-Stokes luminescence of the phosphor under excitation in the range 0.90–0.98 μm. We take advantage of this effect to create a new, efficient “invisible” IR phosphor emitting in the range 1.5–1.6 μm.     

Characterization of <Superscript>4</Superscript>I<Subscript>9/2</Subscript> ↔ <Superscript>4</Superscript>F<Subscript>3/2</Subscript> optical transitions in trivalent Nd<Superscript>3+</Superscript> ions in GaLaS glass

The positions of Stark levels have been determined, using a step-by-step procedure, in the ⁴I_9/2 and ⁴F_3/2 manifolds of Nd³⁺ ions from absorption and photoluminescence measurements in the 12–293 K temperature range. This data has been used to calculate the emission cross-section for which the maximum value turns out to be ～2.3 × 10^?20 cm². The radiative recombination time, calculated using Judd–Ofelt analysis, of the ⁴F_3/2 manifold is in close vicinity to the experimentally determined times that were measured by the conventional decay of PL after interruption of excitation and by QFRS. Moreover, the peak time defined by QFRS is independent of temperature. Therefore, the dominant relaxation mechanism from the ⁴F_3/2 excited manifold of Nd³⁺ ions in GaLaS glass is believed to be by radiative emission.     

Luminescent properties of single-phase Ba<Subscript>2</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>:Tb<Superscript>3+</Superscript>, R (R = Eu<Superscript>2+</Superscript>, Ce<Superscript>3+</Superscript>) phosphors for white LED

The Ba₂P₂O₇:Tb³⁺, R (R?=?Eu²⁺, Ce³⁺) phosphors were synthesized by use of a co-precipitation method. Crystal phase, excitation and emission spectra of sample phosphors are analyzed by means of XRD and FL, respectively. The emission spectra of Ba₂P₂O₇:Ce³⁺, Tb³⁺ phosphors exhibit four linear peaks attributed to the ⁵D₄?→?⁷F_J (J?=?6–3) transition of Tb³⁺ while four broad emission bands are observed in the emission spectra of Ba₂P₂O₇:Eu²⁺, Tb³⁺ phosphors. The effects of Eu²⁺ concentration on the luminescent properties of Ba₂P₂O₇:Tb³⁺, R (R?=?Eu²⁺, Ce³⁺) are studied. Ce³⁺ affects the luminescent properties of Ba₂P₂O₇:Ce³⁺, Tb³⁺ phosphors just as the sensitizer. However, Eu²⁺ is considered both as the sensitizer and the activator in Ba₂P₂O₇:Eu²⁺, Tb³⁺ phosphors. The chromaticity coordinates of Eu²⁺ and Tb³⁺ co-doped phosphors gather around the white light field with the CCT approximate to 5000 K, indicating that the luminescent property of Ba₂P₂O₇:Eu²⁺, Tb³⁺ phosphors may approach to a desired level needed for white LED application.     

Lewis and Brønsted acids in super-acid catalyst SO<Subscript>4</Subscript><Superscript>2−</Superscript>/ZrO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript>

Super-acid catalyst, SO₄ ^2?/ZrO₂–SiO₂, with high zirconium loading was synthesized and the nature of the surface acid was investigated by FT-IR of pyridine adsorption. With the increasing ZrO₂ content, the Lewis and Brønsted acid sites increased and reached the maximum when Zr/Si (molar ratio) = 1.3. The sample with Zr/Si = 1.3 showed the strongest IR adsorption band in the S=O stretching region (1,300–1,400 cm^?1). Pyrosulfate and monosulfate species existed on the surface of the catalysts and the acidic strength could be enhanced by induction effect of their S=O groups. And there were two kinds of Brønsted acid sites on the surface of the catalysts.     

Intense 2.0 µm emission from Ho<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript> co-doped Na<Subscript>5</Subscript>Lu<Subscript>9</Subscript>F<Subscript>32</Subscript> single crystal excited by 980 nm

This paper reported on optical spectra of Na₅Lu₉F₃₂ single crystals co-doped with ~?0.91 mol% Ho³⁺ and various Yb³⁺ concentrations by using an improved Bridgman method. The emission spectra and fluorescence decay curves were measured to investigate the luminescent properties of the Ho³⁺/Yb³⁺ co-doped Na₅Lu₉F₃₂ and the energy transfer process from Yb³⁺ to Ho³⁺ ion. Compared with the Ho³⁺ singly doped Na₅Lu₉F₃₂ crystal, the Ho³⁺/Yb³⁺ co-doped crystal had an obviously enhanced emission at 2.0 µm via the 980 nm laser diode excitation because of the efficient energy transfer from Yb³⁺ to Ho³⁺ ion. The maximum emission intensity at 2.0 µm was obtained at about 6.99 mol% Yb³⁺ concentration when the concentration of Ho³⁺ ions is fixed at ~?0.91 mol% in the current research. The maximum emission cross section of the above sample at 2.0 µm was calculated to be 1.23?×?10^?20 cm² according to the measured emission spectrum. The energy transfer efficiency from Yb³⁺:²F_5/2 to Ho³⁺:⁵I₆ for the crystal was estimated up to 90.8% indicating that Yb³⁺ ions can efficiently sensitize the Ho³⁺ ions.     

Stability of actinide(III,IV) and lanthanide(III,IV) complexes with P<Subscript>2</Subscript>W<Subscript>17</Subscript>O<Stack><Subscript>61</Subscript><Superscript>10−</Superscript></Stack> heteropolyanions

The total stability constants of Th⁴⁺, U⁴⁺, Np⁴⁺, Pu⁴⁺, Am⁴⁺, Cm⁴⁺, Ce⁴⁺, Tb⁴⁺, Pr⁴⁺, Tb³⁺, and Pr³⁺ complexes with P₂W₁₇O ₆₁ ^10? heteropolyanion in 1 M sodium salt solutions at pH ≥ 5.5 (i.e., when the anion is not protonated; so-called “absolute” constants), were determined experimentally or calculated from published data. Plots of constants vs. ionic radius of the f element were considered for solutions with ionic strength 1 (1 M acid or sodium salt solutions at pH ≥ 5.5). The correlations found confirm that the interaction of counterions in the complex is predominantly electrostatic. At the same time, different contributions of the covalent interaction for actinides and lanthanides were suggested.     

Highly Oxygen-Permeable NiV<Subscript>2</Subscript>O<Subscript>6</Subscript>–25 wt % V<Subscript>2</Subscript>O<Subscript>5</Subscript> Molten-Oxide Membrane Material

A NiV₂O₆–25 wt % V₂O₅ molten-oxide material has been prepared and characterized, and its transport properties (electrical conductivity, oxygen ion transport number, and oxygen permeability) have been studied in the temperature range 680–700°C. The results demonstrate that the molten-oxide membrane material obtained possesses high selective oxygen permeability (KO₂ = (2.5–5.6) × 10^–10 mol/(cm s) in the range 680–740°C and \(\frac{{{j_{{O_2}}}}}{{{j_{{N_2}}}}}\) ~ 1500) and can be used in separators for the preparation of extrapure oxygen from air.     

Effect of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> on the dynamics of Li<Superscript>+</Superscript> ions in Li<Subscript>2</Subscript>O·P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

Lithium ion transport has been studied in bismuth lithium phosphate glasses in the frequency range 20 Hz–1 MHz and in the temperature range 423–573 K using impedance spectroscopy. The addition of Bi₂O₃ in Li₂O·P₂O₅ glass is related to the modification of the glass structure and facilitates the Li⁺ ions migration. The ac and dc conductivities, activation energy of the dc conductivity and relaxation frequency are extracted from the impedance spectra. Conductivity of the present glass system is found to be ionic in nature. The electrical response of the glasses has been studied using both conductivity and electric modulus formalisms. A single ‘master curve’ for normalized plots of all the modulus isotherms observed for a given composition indicates the temperature independence of the dynamic processes for ions in these glasses. Nearly identical values of activation energy for dc conduction and for conductivity relaxation time indicate that the ions overcome same energy barrier while conducting and relaxing.     

Cathodoluminescence properties of SiO<Subscript>2</Subscript>:Pr<Superscript>3+</Superscript>and ZnO·SiO<Subscript>2</Subscript>:Pr<Superscript>3+</Superscript> phosphor nanopowders

The successful incorporation of ZnO nanoparticles in Pr³⁺-doped SiO₂ using a sol–gel process is reported. SiO₂:Pr³⁺ gels, with or without ZnO nanoparticles, were dried at room temperature and annealed at 600 °C. On the basis of the X-ray Diffraction (XRD) results, the SiO₂ was amorphous regardless of the incorporation of Pr³⁺ and nanocrystalline ZnO or annealing at 600 °C. The particles were mostly spherical and agglomerated as confirmed by Field Emission Scanning Electron Microscopy. Thermogravimetric analysis of dried gels performed in an N₂ atmosphere indicated that stable phases were formed at ≥900 °C. Absorption bands ascribed to ³H₄-³P_{(J = 0,1,2)}, ¹I₆ and ¹D₂ in the UV–VIS region were observed from SiO₂:Pr³⁺ colloids. The red cathodoluminescent (CL) emission corresponding to the ³P₀ → ³H₆ transition of Pr³⁺ was observed at 614 nm from dried and annealed SiO₂:Pr³⁺ powder samples. This emission was increased considerably when ZnO nanoparticles were incorporated. The CL intensity was measured at an accelerating voltage of 1-5 keV and a fixed beam current of 8.5 μA. The effects of accelerating voltage on the CL intensity and the CL degradation of SiO₂:Pr³⁺ and ZnO·SiO₂:Pr³⁺ were also investigated using Auger electron spectroscopy coupled with an Ocean Optics S2000 spectrometer.     

Synthesis and magnetic properties of M<Subscript>0.08</Subscript>Ti<Subscript>0.91</Subscript>V<Subscript>0.09</Subscript>O<Subscript>2 + δ</Subscript> · <Emphasis Type="Italic">n</Emphasis>H<Subscript>2</Subscript>O (M = Cr,Mn, Fe,Co, Ni) nanopowders

Using sol-gel synthesis and ion exchange, we have prepared titanium vanadium oxide nanopowders doped with transition-metal ions: M_0.08Ti_0.91V_0.09O_{2 + δ} · nH₂O with M = Cr, Mn, Fe, Co, and Ni. The valence state of the ions in the nanopowders and their morphology and structure have been studied by scanning electron microscopy, X-ray diffraction, IR spectroscopy, and X-ray photoelectron spectroscopy. The M _x Ti_0.91V_0.09O_{2 + δ} · nH₂O oxides dried in air or calcined at 400°C in air are shown to be paramagnets. Vacuum annealing of Co_0.08Ti_0.91V_0.09O_{2 + δ} · nH₂O at 700°C gives rise to a significant ferromagnetic contribution.