Phase equilibria in the system Li<Subscript>2</Subscript>O-MgO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>

The subsolidus region of the Li₂O-MgO-B₂O₃ system has been studied by X-ray powder diffraction and differential thermal analysis. Isothermal sections at 500–550 and 650–700°C have been designed. The following complex borates have been found to form: at 500–550°C, Li₂MgB₂O₅ and LiMgBO₃ are formed; at 650–700°C, a new phase Li₄MgB₂O₅ is formed along with LiMgBO₃; and at 5500–600°, Li₂MgB₂O₅ is formed.     

Thermal stability of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>

Differential thermal analysis (DTA) and thermogravimetric analysis (TGA) of an α-Bi₂O₃ sample revealed staged phase transitions in the range 720–800°C (at 720, 780, and 800°C) and the elimination of oxygen to the composition Bi₂O_2.967 during heating to 895°C in air at 16 K/min. In dynamic vacuum (p = 1.33 Pa) at 780–800°C, Bi₂O₃ consecutively transforms to a phase with the cubic γ-Bi₂O₃ structure and tetragonal Bi₂O_2.3?2.4. In the latter, electron diffraction in a transmission electron microscope (ED/TEM) shows a superstructure with the superstructure vector q ₁₁₀ ≈ 1/9, which indicates an ordered arrangement of oxygen vacancies.     

Chemisorption of SO<Subscript>2</Subscript> on the Zn-modified In<Subscript>2</Subscript>O<Subscript>3</Subscript> surface

Chemisorption of SO₂ and O₂ on the In₂O₃ surface containing a zinc additive (0.4–2.7 at.%) was studied in a temperature range of 22–200 °C. At least three forms of sorbed SO₂ exist on the modified In₂O₃ surface. The temperature affects the contribution of single forms of SO₂ sorption and, hence, the change in the electric conductivity. The preliminary sorption of O₂ favors the formation of a donor form of chemisorbed SO₂. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2228–2232, October, 2005.     

Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> phase diagram

Phase relations in the Y₂O₃-Ga₂O₃ system were studied by the anneal-and-quench technique in air within 1000–2300°C, and a phase diagram was plotted. Three compounds were found to form: Y₃GaO₆, Y₄Ga₂O₉, and Y₃Ga₅O₁₂; the temperature and concentration bounds of stability were determined for these compounds. Indexing results for Y₃GaO₆ are given.     

Selective Catalytic Reduction of NO by NH<Subscript>3</Subscript> over MoO<Subscript>3</Subscript> Promoted Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalyst

A series of MoO₃ doped Fe₂O₃ catalysts prepared by the co-precipitation method were investigated in the selective catalytic reduction of NO by NH₃ (NH₃-SCR). The catalysts displayed excellent catalytic activity from 225 to 400°C and high tolerance to SO₂/H₂O poisoning at 300°C. To characterize the catalysts the N₂-BET, XRD, Raman, NO-TPD, NH₃-TPD and in situ DRIFTS were carried out. It was found that the main reason explaining a high NH₃-SCR performance might be the synergistic effect between Fe and Mo species in the catalyst that could enhance the dispersion of Fe₂O₃ and increase NH₃ adsorption on the catalyst surface.     

Phase relations in the MgO-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Phase relations in the MgO-Bi₂O₃-B₂O₃ system have been investigated by X-ray powder diffraction analysis and DTA. No ternary compounds have been found in the system. Quasi-binary sections have been the 600°C determined and isothermal section of the system has been constructed.     

Monolithic FeO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts for ammonia oxidation and nitrous oxide decomposition

(1.2–8.3)%FeO_х/Al₂O₃ monolith catalysts have been prepared by impregnating alumina with aqueous solutions of iron(III) nitrate and oxalate and have been tested in NH₃ oxidation and in the selective decomposition of N₂O in mixtures resulting from ammonia oxidation over a Pt–Rh gauze pack under conditions of nitric acid synthesis (800–900°C). In the case of the support calcined at 1200°C, the catalyst is dominated by bulk Fe₂O₃ particles localized on the Al₂O₃ surface. The activity of these samples in both reactions decreases with a decreasing active component content, thus limiting the potential of Fe₂(C₂O₄)₃ · 5H₂O, an environmentally friendlier but poorly soluble compound, as a substitute for Fe(NO₃)₃ · 9H₂O. Decreasing the support calcination temperature to 1000°C or below leads to the formation of a highly defective Fe–Al–O solid solution in the (1.2–2.7)%FeO_х/Al₂O₃ catalysts. The surface layers of the solid solution are enriched with iron ions or stabilize ultrafine FeO_х particles. The catalytic activity of these samples in both reactions is close to the activities measured for ~8%FeO_х/Al₂O₃ samples prepared using iron nitrate.     

Synthesis,crystal structure,and vibrational spectra of M<Subscript>4</Subscript>V<Subscript>2</Subscript>O<Subscript>3</Subscript>(SO<Subscript>4</Subscript>)<Subscript>4</Subscript> (M = K,Rb, Cs)

Synthesis was performed and physicochemical properties were studied for the M₄V₂O₃(SO₄)₄ complexes, where M = K, Rb, or Cs. Their crystal structures were determined using the set of data from X-ray diffraction and neutron diffraction studies. All compounds crystallize in a triclinic lattice (space group \(P\bar 1\), Z = 2) with the parameters: a = 7.7688(2), 7.8487(1), 8.1234(1) Å; b = 10.4918(3), 10.8750(2), 11.1065(1) Å; c = 11.9783(4), 12.1336(2), and 11.8039(1) Å; α = 76.600(2)°, 77.910(1)°, 79.589(1)°; β = 75.133(2)°, 75.718(1)°, 87.939(1)°; γ = 71.285(2)°, 72.189(1)°, 75.567(1)°; V = 881.78(5), 945.42(3), 1014.34(2) ų for K, Rb, Cs, respectively. The structure of M₄V₂O₃(SO₄)₄ was found to be formed by discrete complex anions V₂O₃(SO₄) ₄ ^4? incorporating two oxygen-bridged vanadium atoms in a distorted octahedral oxygen environment. The sulfate groups are coordinated by the vanadium atoms in the chelating mode with a large scatter of S-O interatomic distances and OSO angles. Every VO₆ octahedron has a short terminal vanadium-oxygen bond with a length of about 1.6Å. The V₂O₃(SO₄) ₄ ^4? complex anions in potassium and rubidium compounds differ from that in Cs₄V₂O₃(SO₄)₄ in the type of symmetry and mutual spatial orientation. The vibrational spectra were presented and interpreted in line with the structural analysis data.     

Solid electrolytes with cesium cation conductivity in the Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiO<Subscript>2</Subscript>-Cs<Subscript>2</Subscript>O system

Solid solutions based on cesium monogallate CsGaO₂ are synthesized in the Ga₂O₃-TiO₂-Cs₂O system. Their crystalline structure and also temperature and concentration conductivity dependences are studied. The cesium cation character of conductivity is confirmed. The most conducting samples contain an excess of cesium oxide and have the structure of high-temperature γ-modification of KAlO₂. Their specific conductivity is (5.0–6.7) × 10^?3 S cm^?1 at 400 °C, (2.5–5.0) × 10^?2 S cm^?1 at 700°C at the activation energy of 33–35 kJ/mol^?1.     

Preparation of CuCr<Subscript>2</Subscript>O<Subscript>4</Subscript> nanopowders using two different chromium sources

CuCr₂O₄ spinel powders were synthesized starting from different chromium sources, namely (i) chromium oxide (α-Cr₂O₃) and (ii) ammonium dichromate ((NH₄)₂Cr₂O₇). The copper source was a Cu(II) carboxylate-type complex. The Cu(II) carboxylate complex was obtained by the redox reaction between Cu(NO₃)₂·3H₂O and 1,3-propanediol (1,3PG) at 130 °C. In the first case (i), we have started from a mixture of α-Cr₂O₃, Cu(NO₃)₂·3H₂O and 1,3PG that upon heating formed the copper malonate complex, which decomposed around 220 °C forming an oxide mixture (CuO + α-Cr₂O₃). In the second case (ii), (NH₄)₂Cr₂O₇, Cu(NO₃)₂·3H₂O and 1,3PG were homogenously mixed. Heating this mixture at 130 °C resulted, in situ, in the Cu(II) complex. On controlled temperature increase, the violent decomposition of (NH₄)₂Cr₂O₇ took place at 180 °C along with the decomposition of the Cu(II) complex, leading to an amorphous oxide mixture of Cr₂O_3+x and CuO. By annealing the samples in the temperature range 400–1000 °C, the spinel phase (CuCr₂O₄) was obtained in both cases: (i) at 800 °C and (ii) at 600 °C as a result of the interactions between the precursors used, when the oxide system was amorphous and highly reactive. The presence of CuCr₂O₄ was highlighted by XRD and FTIR analyses.     

Thermal oxide synthesis and characterization of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanorods and Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanowires

Fe₃O₄ nanorods and Fe₂O₃ nanowires have been synthesized through a simple thermal oxide reaction of Fe with C₂H₂O₄ solution at 200–600°C for 1 h in the air. The morphology and structure of Fe₃O₄ nanorods and Fe₂O₃ nanowires were detected with powder X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The influence of temperature on the morphology development was experimentally investigated. The results show that the polycrystals Fe₃O₄ nanorods with cubic structure and the average diameter of 0.5–0.8 μm grow after reaction at 200–500°C for 1 h in the air. When the temperature was 600°C, the samples completely became Fe₂O₃ nanowires with hexagonal structure. It was found that C₂H₂O₄ molecules had a significant effect on the formation of Fe₃O₄ nanorods. A possible mechanism was also proposed to account for the growth of these Fe₃O₄ nanorods. Supported by the Fund of Weinan Teacher’s University (Grant No. 08YKZ008), the National Natural Science Foundation of China (Grant No. 20573072) and the Doctoral Fund of Ministry of Education of China (Grant No. 20060718010)     

Subsolidus phase relations in the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Li<Subscript>2</Subscript>O-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> (Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>) systems

The phase composition has been studied and an equilibrium phase diagram has been designed for the Al₂O₃-Li₂O-R₂O₅ (R = Ta or Nb) systems in the subsolidus region up to 1000°C and 85 mol % Li₂O. New phases with the composition Li_1+x Al_1?x O_2?x , where x = 0–0.67, have been found.     

Mechanism and kinetics of formation of La<Subscript>2</Subscript>SrFe<Subscript>2</Subscript>O<Subscript>7</Subscript> and Nb<Subscript>2</Subscript>SrFe<Subscript>2</Subscript>O<Subscript>7</Subscript>

Phase formation processes in the systems Ln₂O₃-SrO-Fe₂O₃ (Ln = La, Nd) in air in the temperature range 1200–1500°C were studied. The synthesis of the complex ferrites La₂SrFe₂O₇ and Nb₂SrFe₂O₇ involves the formation of the intermediate compounds LnFeO₃ and LnSrFeO₄ and occurs by the same mechanism as the synthesis of the corresponding aluminates, but much faster.     

Conductivity of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-NiO composites

The conductivity and transport number of oxygen ions of Bi₂O₃-(10, 30, 50) vol % NiO composites are measured using the four-probe and coulomb-volumetric methods at various temperatures. It is shown that the Bi₂O₃-50 vol % NiO composite exhibits a high mixed ionic-electronic conductivity in the temperature range from 730 to 800°C.     

Phase relations in the CaO-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> system in the subsolidus region

Phase relations in the CaO-Bi₂O₃-B₂O₃ system have been investigated by X-ray powder diffraction and differential thermal analyses, and the isothermal section at 600°C has been constructed. The formation of ternary compounds at the component ratios 1CaO: 1Bi₂O₃: 1B₂O₃ (CaBi₂B₂O₇) and 1CaO: 1Bi₂O₃: 2B₂O₃ (CaBi₂B₄O₁₀) has been established X-ray diffraction characteristics of these phases are presented.     

Thermal stability of layered perovskite-like oxides NaNdTiO<Subscript>4</Subscript> and Na<Subscript>2</Subscript>Nd<Subscript>2</Subscript>Ti<Subscript>3</Subscript>O<Subscript>10</Subscript>

Thermal stabilities of layered perovskite-like oxides NaNdTiO₄ and Na₂Nd₂Ti₃O₁₀ were studied in the temperature ranges from 780 to 1100°C and from 1100 to 1400°C, respectively. Chemical mechanism of their thermal decomposition was proposed. Higher thermal stability of Na₂Nd₂Ti₃O₁₀ was rationalized on the basis of crystallochemical data.     

Physicochemical properties and mixed electronic and ionic conduction of composite ceramics in the system ZrO<Subscript>2</Subscript>-Bi<Subscript>2</Subscript>CuO<Subscript>4</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>

Composites ZrO₂-(Bi₂CuO₄+ 20 wt % Bi₂O₃) (50–80 vol % ZrO₂) are synthesized and their physicochemical properties are studied. It is demonstrated that the composites comprise triple-phase mixtures of ZrO₂ of a monoclinic modification, Bi₂CuO₄, and solid solution Bi_2?x Zr _x O_{3 + x/2} and retain their mechanical strength up to 800°C. Impedance spectroscopy is used to examine their electroconductivity at 700–800°C in the interval of partial oxygen pressures extending from 37 to 2.1 × 10⁴ Pa. Contributions made by electronic and ionic constituents to their overall conductivity are evaluated. The best specimens’ conductivity is ～0.01 S cm^?1, with the electronic and ionic transport numbers nearly equal. The composite consisting of 50 vol % ZrO₂ and 50 vol % (Bi₂CuO₄ + 20 wt % Bi₂CuO₄) is tested in the role of an oxygen-separating membrane. The selective flux of oxygen in the temperature interval 750–800°C amounts to (2.2–6.3) × 10^?8 mol cm^?2 s^?1, testifying that these materials may be used as gas-separating membranes.     

Preparation and characterization of H<Subscript>3</Subscript>PW<Subscript>12</Subscript>O<Subscript>40</Subscript>/ZrO<Subscript>2</Subscript> catalyst for carbonation of methanol into dimethyl carbonate

A H₃PW₁₂O₄₀/ZrO₂ catalyst for effective dimethyl carbonate (DMC) formation via methanol carbonation was prepared using the sol–gel method. X-ray photoelectron spectra showed that reactive and dominant (63%) W(VI) species, in WO₃ or H₂WO₄, enhanced the catalytic performances of the supported ZrO₂. The mesoporous structure of H₃PW₁₂O₄₀/ZrO₂ was identified by nitrogen adsorption–desorption isotherms. In particular, partial sintering of catalyst particles in the duration of methanol carbonation caused a decrease in the Brunauer–Emmett–Teller surface area of the catalyst from 39 to 19 m²/g. The strong acidity of H₃PW₁₂O₄₀/ZrO₂ was confirmed by the desorption peak observed at 415 °C in NH₃ temperature-programmed desorption curve. At various reaction temperatures (T?=?110, 170, and 220 °C) and CO₂/N₂ volumetric flow rate ratios (CO₂/N₂?=?1/4, 1/7, and 1/9), the calculated catalytic performances showed that the optimal methanol conversion, DMC selectivity, and DMC yield were 4.45, 89.93, and 4.00%, respectively, when T?=?170 °C and CO₂/N₂?=?1/7. Furthermore, linear regression of the pseudo-first-order model and Arrhenius equation deduced the optimal rate constant (4.24?×?10^?3 min^?1) and activation energy (E_a?=?15.54 kJ/mol) at 170 °C with CO₂/N₂?=?1/7 which were favorable for DMC formation.     

Interaction of Cl<Subscript>2</Subscript> and SO<Subscript>2</Subscript> with Finely Divided In<Subscript>2</Subscript>O<Subscript>3</Subscript>

The effect of O₂, Cl₂, and SO₂ on electrophysical and sorption properties of powdered In₂O₃ with a large specific area is studied at 23–200°C. The specimen is most sensitive to Cl₂ and SO₂ at near-room temperatures.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 529–536.Original Russian Text Copyright © 2005 by Vinokurova, Derlyukova.     

The synthesis and selected properties of Co<Subscript>2</Subscript>InV<Subscript>3</Subscript>O<Subscript>11</Subscript>

It has been demonstrated that Co₂V₂O₇ and InVO₄ react with each other forming a new compound of the Co₂InV₃O₁₁ formula, when their molar ratio is equal to 1:1, or among CoCO₃, In₂O₃ and V₂O₅, mixed at a molar ratio of 4:1:3. This compound melts incongruently at the temperature of 960±5°C, depositing crystals of InVO₄. It crystallizes in the triclinic system and the unit cell parameters amount to: a=0.6524(6) nm, b=0.6885(5) nm, c=1.0290(4) nm, α=96.5°, β=104.1°, γ=100.9°, Z=2. The phase equilibria being established in the Co₂V₂O₇–InVO₄ system over the whole components concentration range up to the solidus line were described.