Ba－K－Bi－O超导体的化学稳定性

Ba-K-Bi-O (BKBO)超导体的导电性和超导性各向同性,相干长度长,制备温度低,因此它有良好的应用前景.但在BKBO超导器件走向实用化时,还必须了解它在环境介质中的化学稳定性,以便采取相应的保护措施.本文目的就是研究BKBO在各种介质中的稳定性及其作用机理.用电化学法在BKBO膜上制成了聚毗咯((PPy)和聚唾吩((PTh)膜,为BKBO超导器件的保护提供了新思路.     

Ba—K—Bi—O和Ba—K—Pb—O氧化物的磺量滴定

本文提出了碘量法滴定Ｂａ－Ｋ－Ｂｉ－Ｏ和Ｂａ－Ｋ－Ｐｂ－Ｏ氧化物中Ｂａ和Ｐｂ的名义价态，然后据此计算这些氧化物中Ｋ和Ｂａ含量的方法。     

New Phase in the Bi–Sr–Ca–Cu–O System

Cooling a melt of a Bi–Sr–Ca–Cu–O system (Bi:Sr:Ca:Cu = 4:3:3:4 or 2:2:2:4) from 1000°C-1050°C yielded crystals of a new red-colored nonsuperconducting phase, accompanying the superconducting 2212 and 2201 phases. Based on the EPR spectra, it was concluded that copper is univalent in this compound. The new phase has a composition Bi_2.2Sr_1.6Ca_1.3Cu₂Ox. The X-ray diffraction pattern has been indexed, and the unit cell parameters of the phase have been determined: space group P2/m, a = 12.93, b = 4.55, c = 10.94 ; = 102.72°.     

Ba—Pb—O和Bi—Pb—O的电化学合成和表征

本文研究了用电化学方法在水溶液中合成铅基氧化物Ｂａ－Ｐｂ－Ｏ和Ｂｉ－Ｐｂ－Ｏ的方法，并采用ＸＰＳ，ＸＲＤ和ＥＤＸ对电合成产物进行了表征。     

Specific features of phase equilibriums in Ln–Ba–Fe–O systems

Formation of five-layered Ln_2–εBa_3+εFe₅O_15–δ phases [exhibiting nanoscale ordering with layer-by-layer location of the cations in the Ln–Ba–(Ln,Ba)–(Ln,Ba)–Ba–Ln perovskite-type structure] has occurred in the Ln–Ba–Fe–O (Ln = Y, Pr, Nd, Sm, Eu, and Gd) systems at 1100°С in air. Partial substitution of iron with cobalt (Ln_2–εBa_3+εFe_5–yCo_yO_15–δ, Ln = Nd, Sm, Eu) has stabilized formation of the ordered structure. The oxygen content in the complex oxides has been determined in air over a wide temperature range by means of high-temperature thermogravimetry and iodometric titration. The change in oxygen content with temperature for the phases with five-layered ordering was significantly smaller than for the disordered phases.     

Impedance spectroscopy of V2O5–Bi2O3–BaTiO3 glass–ceramics

The glasses within composition as: (80 − x)V₂O₅/20Bi₂O₃/xBaTiO₃ with x = 2.5, 5, 7.5 and 10 mol% have been prepared. The glass transition (T_g) increases with increasing BaTiO₃ content. Synthesized glasses ceramic containing BaTi₄O₉, Ba₃TiV₄O₁₅ nanoparticles of the order of 25–35 nm and 30–46 nm, respectively were estimated using XRD. The dielectric properties over wide ranges of frequencies and temperatures were investigated as a function of BaTiO₃ content by impedance spectroscopy measurements. The hopping frequency, ω_h, dielectric constant, ε′, activation energies for the DC conduction, E_σ, the relaxation process, E_c, and stretched exponential parameter β of the glasses samples have been estimated. The, ω_h, β, decrease from 51.63 to 0.31 × 10⁶ (s⁻¹), 0.84 to 0.79 with increasing BaTiO₃ respectively. Otherwise, the E_σ, increase from 0.279 to 0.306 eV with increasing BaTiO₃. The value of dielectric constant equal 9.5·10³ for the 2.5BaTiO₃/77.5V₂O₅/20Bi₂O₃ glasses-ceramic at 330 K for 1 KHz which is ten times larger than that of same glasses composition. Finally the relaxation properties of the investigated glasses are presented in the electric modulus formalism, where the relaxation time and the respective activation energy were determined.     

ELECTRODEPOSITION OP Ba－K－Bi－O AND Ba－K－M－Bi－O （M＝Rb， Pb AND La） SINGLE CRYSTALS

ＥＬＥＣＴＲＯＤＥＰＯＳＩＴＩＯＮＯＰＢａ－Ｋ－Ｂｉ－ＯＡＮＤＢａ－Ｋ－Ｍ－Ｂｉ－Ｏ（Ｍ＝Ｒｂ，ＰｂＡＮＤＬａ）ＳＩＮＧＬＥＣＲＹＳＴＡＬＳ￥ＬｉａｎｇＺｈｏｎｇＺＨＡＯ；ＪｉｎＢｉａｏＺＨＡＮＧ；ＷｅｉＨｕａＷＡＮＧＳｈｉＨｏｎｇＬＩＵ；ＤａｏＢｅ...     

The Thermal Synthesis of the ZnO–Bi2O3 Pigments

A zinc oxide pigment with an admixture of bismut oxide has been prepared as new yellow pigment for colouring of plastics and paints. The effect of the Bi₂ O₃ in the starting mixture on the colour hue of the pigment has been evaluated. The calcination conditions of the pigment synthesis have been established. The synthesis of these pigments was followed by thermal analysis using a derivatograph apparatus in our laboratory. The optimum conditions for the synthesis of pigments and the properties of the products have been estimated. This revised version was published online in August 2006 with corrections to the Cover Date.     

Infrared,Raman and XPS spectroscopic studies of Bi2O3–B2O3–Ga2O3 glasses

Glasses with compositions 60Bi₂O₃–(40?x)B₂O₃–xGa₂O₃ (x = 5, 10, 15, 20 mol%) are prepared by conventional melting method. The thermal properties are investigated by differential thermal analysis (DTA) and the structures of the glasses were probed by Infrared, Raman and X-ray photoelectron spectroscopy (XPS). The results show that density, refractive index and optical basicity increase with the increase of Ga₂O₃. The glass transition temperature (T_g), the onset crystallization temperature (T_x), ΔT (T_x?T_g) decrease with the content of Ga₂O₃. The cut-off edges in ultraviolet and infrared shift to longer wavelength with the increase of Ga₂O₃. On the other hand, the addition of Ga₂O₃ causes a progressive coordination number change of the boron atom from 3 to 4. XPS result indicates both Bi⁵⁺ and Bi³⁺ exist in 5 mol% Ga₂O₃ content, while Bi⁵⁺ amounts decrease with the increase of Ga₂O₃ contents. The glass is mainly composed of [BiO₆], [BO₃], [BO₄] and [GaO₄] polyhedra. Glasses are supposed to have layer structure. [BO₃] triangle and [BO₄] tetrahedra may be located between the [GaO₄] tetrahedral and [BiO₆] octahedra to prevent crystallization and to compensate electric charge.     

Characterization of sol–gel process in the Y–Ba–Cu–O acetate–tartrate system using IR spectroscopy

Systematic investigation of sol–gel process in the Y–Ba–Cu–O acetate–tartrate system was performed using IR spectroscopy. Different values of synthesis parameters (temperature and duration of inorganic polymerization reactions, evaporation temperature and evaporation time during gelation) were used, and significant influence in some cases on superconducting characteristics of the oxide ceramics of composition YBa₂Cu₄O₈ was observed. Characterization by IR spectroscopy and thermogravimetric analysis, revealed the difference of local homogeneity in the precursor gels prepared under different evaporation regimes during gelation process. In addition, the explanation of the possible hydrolysis and condensation reactions in the sol state has been suggested.     

Infrared,Raman and XPS spectroscopic studies of Bi2O3–B2O3–GeO2 glasses

Glasses with composition 50Bi₂O₃–(50 ? x) B₂O₃–xGeO₂ (x = 0, 5, 10, 15 mol%) were prepared by conventional melting method. The thermal properties were investigated by differential thermal analysis (DTA) and the structures of the glasses were probed by Infrared, Raman and X-ray photoelectron spectroscopy (XPS). The results show that density, refractive index and optical basicity increase with the increase of GeO₂. The glass transition temperature (T_g), onset crystallization temperature (T_x) and ΔT (T_x ? T_g) increase as well. The cut-off edges in ultraviolet and infrared shift to longer wavelength by the addition of GeO₂. Infrared, Raman and XPS results indicate that the glass network consists of [Bi–O₆] octahedron, [BO₃] triangle, [BO₄] tetrahedron and [GeO₄] tetrahedron and borate oxide mainly exists in [BO₃] units. XPS result indicates Ge⁴⁺ ions form steady [GeO₄] tetrahedra units in the glass network and the number of non-bridging oxygens decreases with the addition of GeO₂.     

209Bi NQR in Mixed Oxides 2Bi2O3· B2O3, 3Bi2O3· 5B2O3, and Bi2O3· 3B2O3

It was earlier found from nuclear quadrupole resonance (NQR) measurements and computer modeling that -Bi₂O₃, Bi₃O₄Br and mixed oxides Bi₂O₃· 2Al₂O₃, Bi₂O₃· 2Ga₂O₃, Bi₂O₃· 3GeO₂, and 2Bi₂O₃· 3GeO₂exhibit local ordered magnetic fields from 30 to 200 G. It thus follows that these compounds are not diamagnets in a conventional sence of the word. With the aim of revealing previously unknown magnetic properties in bismuth(III) oxide-based Main Group element compounds, the mixed bismuth–boron oxides 2Bi₂O₃· B₂O₃, 3Bi₂O₃· 5B₂O₃, and Bi₂O₃· 3B₂O₃were prepared and studied using ²⁰⁹Bi NQR. The quadrupole interactions of the ²⁰⁹Bi nuclei and their electronic environment were studied, the crystallochemical features of the compounds were discussed, and the conformity of the ²⁰⁹Bi results to the X-ray structure data was verified. The preliminary tests in the field of a permanent magnet showed that the resonance intensities increase in external magnetic fields, indicating that a magnetism of unknown nature develops in the titled compounds. It was found reasonable to continue studies of the magnetic properties of these compounds using single-crystal ²⁰⁹Bi NQR in external magnetic fields.     

Synthesis and structural investigation of a unique columnar phase in the Bi2O3–TeO2–V2O5 System

A new columnar phase Bi(11.65)Te(1.35)V(5)O(34-δ) (δ ～ 1.3) containing VO(4) tetrahedra has been identified for the first time in the Bi(2)O(3)-TeO(2)-V(2)O(5) system. The phase formation and the extent of substitution of Te(4+) for Bi(3+) ions in order to stabilize V(5+) in this composition have been confirmed by the single crystal analysis, combined with the powder X-ray diffraction of the solid state synthesized bulk crystalline samples. The oxide crystallizes in a monoclinic crystal system, space group P2/c, with unit cell parameters a = 11.4616(7) ?, b = 5.7131(3) ?, c = 23.5090(18) ?, β = 101.071° (6) (Z = 2). The structure retains the basic features of the columnar oxides with the presence of [Bi(10.65)Te(1.35)O(14)](n)(9.35n+) columns along the (010) direction, surrounded by (VO(4)) tetrahedra placed in the planes parallel to (100) and (001), with an isolated bismuth atom in between the columns. The composition with a limited Te(4+) substitution, Bi(11.65)Te(1.35)V(5)O(34-δ) (δ ～ 1.3), exists with a surprisingly high oxygen deficiency as compared to the stoichiometrically known columnar oxides such as Bi(13)Mo(4)VO(34), Bi(12)Te(1)Mo(3)V(2)O(34), and Bi(11)Te(2)Mo(2)V(3)O(34). The structure of this interesting member of the columnar family of oxides based on the single crystal X-ray diffraction and the Raman spectroscopic studies indicates the possibility of the distribution of the oxygen vacancies among the VO(4) tetrahedral units. Further confirmation for the formation of vanadium stabilized columnar structures has been provided by the successful preparation of Bi(11.65)Te(1.35)V(4)CrO(34-δ) (δ ～ 0.83) and Bi(11.65)Te(1.35)V(4)WO(34-δ) (δ ～ 0.83) phases. Preliminary investigation of the photocatalytic efficiencies of the oxides Bi(11.65)Te(1.35)V(5)O(34-δ), Bi(11.65)Te(1.35)V(4)CrO(34-δ), and Bi(11.65)Te(1.35)V(4)WO(34-δ) revealed moderate photocatalytic activities for the decomposition of the dyes such as Rhodamine B under UV-vis light irradiation.     

Fe3O4–SiO2–Bi2O3-catalyzed One-Pot Synthesis of Tetrahydrobenzo[b]pyran Derivatives Under Solvent-Free Conditions

Russian Journal of Organic Chemistry - A Fe3O4–SiO2–Bi2O3 magnetic nanocatalyst was used to synthesize tetrahydrobenzo[b]pyran derivatives from malononitrile, cyclohexane-1,3-dione, and...     

Catalytic Properties of the Fe2O3–Bi2O3 System in Ammonia Oxidation to Nitrogen Oxides

The catalytic properties of the Fe₂O₃–Bi₂O₃ system in ammonia oxidation are studied at 1073 K. The effect of phase composition on the physicochemical and catalytic properties of the system is determined. The catalytic properties of individual components of the system (-Fe₂O₃, Bi₂Fe₄O₉, BiFeO₃, and -Bi₂O₃) are studied.     

Crystal structure of natural Ag–Cu–Pb–Bi sulfide

The crystal structure of a natural sulfide Cu_3,44Ag_0,56Pb₂Bi₆S₁₃ (Сmcm, Z = 4, a = 3.973(1) Å, b = 13.370(2) Å, c = 42.182(7) Å, R = 0.059) is determined. The structure has seven cation positions: two of them (Cu and Ag) are in a tetrahedral environment of sulfur atoms; one (Pb), in a special position (mm2), has a coordination polyhedron in the form of a bicapped trigonal prism; and the other cation positions are surrounded by sulfur atoms forming distorted octahedra. The mirror symmetry plane perpendicular to the c translation causes microtwinning by cutting a layer of trigonal prisms framed by tetrahedron ribbons. These layers are divided by those composed by edge-linked octahedra with a diagonal ribbon of five octahedra (N = 5). The cation and anion positions are ordered by individual sublattices with pseudohexagonal subcells on the m planes perpendicular to the a translation, which concentrate the positions of all the atoms. Supposedly, this natural sulfide is the previously described (1885) yet unconfirmed alaskaite mineral from the lillianite–heyrovskyite homological series and may be isostructural to the ourayite mineral.     

Bi–O–Si键作为热电子传输通道增强SiO2@Bi微球的等离子体光催化效率

具有等离子体效应的贵金属Au和Ag等常被用于修饰半导体光催化剂.非贵金属Bi成本低,来源丰富,最近被报道可以直接作为等离子体光催化剂应用于空气中NO净化.为了进一步提高Bi单质的光催化活性,需对其进行改性.SiO2的禁带宽度过大,不能单独作为光催化剂,但它的稳定性好,比表面积大,因而常作复合材料用于提高光催化剂的反应效率、稳定性及对反应物的吸附能力.目前,尚未见SiO2修饰Bi单质的相关报道.本文通过溶剂热法制备了SiO2@Bi微球,并对其微结构进行了表征,对光催化氧化NO的反应过程进行了原位漫反射红外光谱(DRIFTS)分析,揭示了Bi–O–Si键在提升SiO2@Bi光催化氧化NO性能中的作用机制.结果显示,用SiO2纳米颗粒修饰Bi球,形成的Bi–O–Si键作为热电子传输通道,能显著提高Bi单质光催化氧化去除NO的能力.扫描电镜、透射电镜、傅里叶变换红外光谱和X射线光电子能谱等表征结果表明,SiO2纳米颗粒负载于Bi球上,且SiO2@Bi内形成了Bi–O–Si键.作为光生热电子的传输通道,Bi–O–Si键能促进光生电子的转移和载流子的分离,提高活性自由基?OH和?O2?的产量,增强SiO2@Bi在紫外光下等离子体光催化氧化NO的能力.自由基捕获测试(ESR)表明,SiO2@Bi在光催化反应中产生的?OH和?O2?数量均明显高于单质Bi在反应中形成自由基的数量.原位DRIFTS发现,Bi–O–Si键能快速转移光生电子,从而有利于NO→NO2→NO3?反应的进行.此外,SiO2@Bi的比表面积变大,因而对NO的吸附能力增强,同时促进了光催化反应.本文揭示了SiO2@Bi等离子体光催化性能增强的微观机制和光催化氧化NO的反应机理,为Bi基光催化剂的改性和应用提供了新的认识.