High n-value phases in the complex bismuth oxides with layered structure,Bi2CaNan−2NbnO3n+3

Complex bismuth oxides with layered structure are prepared with a series of compositions in the system Bi₂CaNb₂O₉-NaNbO₃. It is found by X-ray powder diffraction that each compound is composed of more than two phases, which are described by a formula Bi₂CaNa_n?2Nb_nO_3n+3, e.g., in the sample with the nominal composition Bi₂CaNb₂O₉ · 8NaNbO₃, the phases with n = 6 to 8 appear predominantly. These phases are closely intergrown to each other. Moreover, high-resolution electron microscopy reveals that microsyntactic intergrowth frequently occurs in the phases with n > 5. The occurrence of the latter intergrowth is explained in terms of the bond length obtained.     

Synthesis, Electrical Properties, and Powder Neutron Crystal Structure Refinement of Pb1−xBixPt2O4 Compounds (0≤x≤0.3)

Substitution of Pb for Bi in the recently characterized mixed-valence lead-platinum oxide PbPt₂O₄ was attempted and a Pb_1−xBi_xPt₂O₄ solid solution was obtained for 0≤x≤0.3. Powder X-ray diffraction study showed that all substituted compounds crystallize with similar triclinic unit cell and PbPt₂O₄ lattice parameters. The structural model of Pb_0.7Bi_0.3Pt₂O₄ was refined from powder X-ray diffraction data using the Rietveld method and the results indicate the same crystal structure than PbPt₂O₄ with one mixed Pb/Bi atomic site. Neutron diffraction realized on the two limit compositions of the solid solution (x=0 and 0.3) allowed to confirm the PbPt₂O₄ and Pb_0.7Bi_0.3Pt₂O₄ stoichiometries. Mean oxidation degree of Pt atoms in the [PtO₄] infinite chains decreases from +3 for PbPt₂O₄ to +2.7 for Pb_0.7Bi_0.3Pt₂O₄. Conductivity measurements show a metallic behavior for all the compositions except the limit composition x=0.3 for which a semiconducting behavior appears.     

Series of compositions Bi2(M′xM1−x)4O9 (M′, M=Al, Ga, Fe; 0≤x≤1) with mullite-type crystal structure: Synthesis, characterization and O/O exchange experiment

Series of compositions Bi₂(M′_xM_1−x)₄O₉ with x=0.0, 0.1,…, 1.0 and M′/M=Ga/Al, Fe/Al and Fe/Ga were synthesized by dissolving appropriate amounts of corresponding metal nitrate hydrates in glycerine, followed by gelation, calcination and final heating at 800 °C for 24 h. The new compositions with M′/M=Ga/Al form solid-solution series, which are isotypes to the two other series M′/M=Fe/Al and Fe/Ga. The XRD data analysis yielded in all cases a linear dependence of the lattice parameters related on x. Rietveld structure refinements of the XRD patterns of the new compounds, Bi₂(Ga_xAl_1−x)₄O₉ reveal a preferential occupation of Ga in tetrahedral site (4 h). The IR absorption spectra measured between 50 and 4000 cm⁻¹ of all systems show systematic shifts in peak positions related to the degree of substitution. Samples treated in ¹⁸O₂ atmosphere (16 h at 800 °C, 200 mbar, 95% ¹⁸O₂) for ¹⁸O/¹⁶O isotope exchange experiments show a well-separated IR absorption peak related to the M-¹⁸O_c-M vibration, where O_c denotes the common oxygen of two tetrahedral type MO₄ units. The intensity ratio of M-¹⁸O_c/M-¹⁶O_c IR absorption peaks and the average crystal sizes were used to estimate the tracer diffusion coefficients of polycrystalline Bi₂Al₄O₉ (D=2×10⁻²² m²s⁻¹), Bi₂Fe₄O₉ (D=5×10⁻²¹ m²s⁻¹), Bi₂(Ga/Al)₄O₉ (D=2×10⁻²¹ m²s⁻¹) and Bi₂Ga₄O₉ (D=2×10⁻²⁰ m²s⁻¹).     

A new bismuth potassium nitrate oxide, Bi1.7K0.9O2(NO3)2: Synthesis, structure, thermal behavior, and photocatalytic properties

We report here the first observation of a bismuth potassium nitrate Bi_1.7K_0.9O₂(NO₃)₂, obtained via thermal decomposition of bismuth and potassium nitrate mixtures. The new compound is orthorhombic, space group Immm (71), Z = 2, with a = 3.8698(7) Å, b = 3.8703(7) Å, and c = 24.1271(4) Å. Its crystal structure was refined from powder X-ray diffraction data by analogy with the mineral beyerite, Bi₂O₂Ca(CO₃)₂. The morphology and elemental composition of Bi_1.7K_0.9O₂(NO₃)₂ were characterized using scanning electron microscopy (SEM) with energy dispersive X-Ray spectroscopy (EDS). Its phase transformations upon heating and products of its thermal decomposition were studied using XRD, TGA and FTIR. At 440 °C, Bi_1.7K_0.9O₂(NO₃)₂ transforms to another basic bismuth potassium nitrate with demonstrates a very similar XRD pattern but slightly larger cell parameters. At 520 °C, the intermediate oxide nitrate decomposes into a mixture of crystalline α-Bi₂O₃ and KNO₃. The as prepared Bi_1.7K_0.9O₂(NO₃)₂ showed lower than TiO₂ (Degussa P25) photocatalytic activity upon decomposition of a widely used model pollutant, Rhodamine B (RhB) and photooxidation of potassium iodide under UV-vis light irradiation. Interaction with potassium iodide in alkaline media resulted in formation of Bi₅O₇I.     

Synthesis, Structures, and Thermal Expansion of the La2W2−xMoxO9 Series

The La₂W_2−xMo_xO₉ series has been synthesized by the ceramic method. An alternative synthesis using microwave radiation is also reported. La₂W₂O₉ has two polymorphs and the low-temperature phase (α) transforms to the high-temperature form (β) at 1077°C. The influence of the W/Mo substitution in this phase transition has been investigated by DTA. The β structure for x≥0.7 compositions can be prepared as single phase at any cooling rate. The β phase for 0.3≤x≤0.7 compounds can be prepared as single phase by quenching, whereas a mixture of α and β phases is obtained by slow cooling. The W/Mo ratio in both coexisting phases is different with the β-phase having a higher Mo content. The x=0.1 and 0.2 compounds have been prepared as mixtures of phases. The room temperature structure of β-La₂W_1.7Mo_0.3O₉ has been analyzed by the Rietveld method in P2₁3 space group. The final R-factors were R_WP=9.0% and R_F=5.6% with a structure similar to that of β-La₂Mo₂O₉. Finally, the thermal expansion of both types of structures has been determined from a thermodiffractometric study. The thermal expansion coefficients were 2.9×10⁻⁶ and 9.7×10⁻⁶°C⁻¹ for α-La₂W₂O₉ and β-La₂W_1.2Mo_0.8O₉, respectively.     

Thermal,structural and electrical studies of bismuth zinc borate glasses

Bismuth Zinc Borate glasses with compositions xBi₂O₃–30ZnO–(70 − x)B₂O₃ (where x = 30, 35, 40 and 45 mol %) have been prepared by melt quenching method. These glasses were characterized by X-ray diffraction (XRD), Differential Thermal Analysis (DTA), Fourier Transform Infrared Spectrometer (FTIR) and Broad Band Dielectric Spectrometer (BDS). DTA and FTIR analysis reveals that Non-Bridging Oxygens (NBOs) increase with increase of bismuth content in the glass. Electrical data have been analyzed in the framework of impedance and modulus formalisms. The activation energy for dc conductivity decreases with increase of bismuth concentration. The imaginary part of modulus spectra has been fitted to non-exponential Kohlrausch–Williams–Watts (KWW) function and the value of the stretched exponent (β) is found to be almost independent of temperature but slightly dependent on composition.     

Effect of Niobium doping on structural, thermal, sintering and electrical properties of Bi4V1.8Cu0.2O10.7

Doping Bi₄V_1.8Cu_0.2O_10.7 with niobium has led to the formation of the Bi₄V_1.8Cu_0.2−xNb_xO_10.7+3x/2 solid solution. X-ray diffraction and thermal analysis have shown that only the compound with x=0.05 presents a tetragonal symmetry with a γ^′ polymorph while the other compositions are of β polymorph. The influence of sintering temperature on the microstructure of the samples was investigated by the scanning electron microscopy (SEM). The ceramics sintered at temperatures higher than 820 °C present micro-craks. The evolution of the electrical conductivity with temperature and the degree of substitution has been investigated by impedance spectroscopy. Among all compositions studied the sample with x=0.05 presents the highest value of the conductivity.     

The influence of sulfur substitution on the atomic displacement in Bi2Ti2O7

To clarify the role of A₂O′ and B₂O₆ networks on cation displacement observed in Bi₂Ti₂O′O₆, we used density functional theory calculations to examine the effect of sulfur substitution on the O′ and O sites on lone pair formation and resulting atomic displacement observed in Bi₂Ti₂O′O₆. Cation displacement in bismuth titanate is suppressed only when S is substituted on the O′ site. Analysis of the electronic structure shows that S substitution on the O′ site suppresses the formation of the asymmetric p-type lone pair by modifying the Bi-anion hybridization. Lone pair formation is favored in Bi₂Ti₂O′S₆ and the atomic displacement is larger than that observed in Bi₂Ti₂O′O_6. This enhanced displacement is due to weaker Bi-S versus Bi-O interactions leading to significantly stronger hybridization between the Bi and O′ states in Bi₂Ti₂O′S₆. We also induced lone pair formation in a metallic bismuth pyrochlore oxide (Bi₂Ru₂O′O₆) by modifying the Bi-O interactions through S substitution on the B₂O₆ network, indicating atomic displacement on the A₂O′ network may be achieved by modifying the B₂O₆ network.     

XRD and Si MAS-NMR spectroscopy across the β-Lu2Si2O7-β-Y2Si2O7 solid solution

Samples in the system Lu_2−xY_xSi₂O₇ (0?x?2) have been synthesized following the sol-gel method and calcined to 1300 °C, a temperature at which the β-polymorph is known to be the stable phase for the end-members Lu₂Si₂O₇ and Y₂Si₂O₇. The XRD patterns of all the compositions studied are compatible with the structure of the β-polymorph. Unit cell parameters are calculated as a function of composition from XRD patterns. They show a linear change with increasing Y content, which indicates a solid solubility of β-Y₂Si₂O₇ in β-Lu₂Si₂O₇ at 1300 °C. ²⁹Si MAS NMR spectra of the different members of the system agree with the XRD results, showing a linear decrease of the ²⁹Si chemical shift with increasing Y content. Finally, a correlation reported in the literature to predict ²⁹Si chemical shifts in silicates is applied here to obtain the theoretical variation in ²⁹Si chemical shift values in the system Lu₂Si₂O₇-Y₂Si₂O₇ and the results compare favorably with the values obtained experimentally.     

Phase relationships in the system SrBr2SrCl2

Strontium bromide-chloride phases (SrBr_xCl_2?x) in the composition region 2.00 > x > 0 were prepared and examined by the Guinier powder X-ray diffraction technique. Observed and calculated powder intensities for the compositions x = 1.60, 1.40, and 0.30 are presented. The anions assume an ordered arrangement at the first two compositions and a random arrangement at the third. Two previously unreported intermediate phases at the composition about x = 1.50 and x = 0.60, both of unknown structure, were identified and their d values are reported. SrBr₂ is found to be insoluble in SrCl₂.     

Thermally stimulated crystallization of (20−x)LiO2-80TeO2-xWO3 glass system

Tellurite glasses of the (20−x)LiO₂-80TeO₂-xWO₃ system were synthesized (x=0, 5, and 10) and annealed at different temperatures, and the crystallization kinetics was studied using XRD, FTIR spectroscopy, and DSC techniques. XRD data evidenced the amorphous state of as-quenched samples, while thermally treated samples showed the growth of crystalline phases. FTIR spectroscopy was used to observe the evolution of the vibrational mode assigned to the TeO₂ phases. The presence of γ-TeO₂, α-TeO₂, and α-Li₂Te₂O₅ crystalline phases was observed for the sample TL, x=0, while only the first and second phases were observed for TLW5 and TLW10 samples, x=5 and 10, respectively, suggesting that WO₃ enters the structure preferentially as glass former, inhibiting the growth of the phase α-Li₂Te₂O₅.     

[Bi6O4.5(OH)3.5]2(NO3)11: a new anhydrous bismuth basic nitrate. Synthesis and structure determination from twinned crystals

The bismuth basic nitrate [Bi₆O_4.5(OH)_3.5]₂(NO₃)₁₁ crystallizes in the monoclinic space group P2₁ with , , , β=107.329(17)° and . Its structure has been determined from , twinned crystal X-ray data (16 781 reflections, 683 parameters, R=0.0703). It is built upon [Bi₆O_x(OH)_8−x]^(10−x)+, x=4 and x=5 hexanuclear complexes and nitrate groups. The polycationic entities are linked to the nitrate anions either by hydrogen bonds or through bismuth-oxygen coordination. Even at , the [Bi₆O₄(OH)₄]⁶⁺ and [Bi₆O₅(OH)₃]⁵⁺ polycations could not be observed as such, the crystal structure refinement only detecting an average [Bi₆O_4.5(OH)_3.5]^5.5+ polycation. To prove the presence of both hexanuclear complexes in the structure, we report the existence of a correlation between the bismuth-linked oxygen bond-valence parameters and the presence, or not, of hydroxyl groups. Moreover, the Raman spectrum of the new anhydrous bismuth basic nitrate is compared to those of [Bi₆O₅(OH)₃](NO₃)₅·3H₂O, [Bi₆O₄(OH)₄](NO₃)₆·4H₂O, and two yet uncharacterized bismuth nitrates.     

Microstructural and transport properties in substituted Bi2Sr2CaCu2O8+δ-modulated compounds

X-ray powder diffraction and resistivity measurements were performed on Bi₂Sr₂CaCu₂O_8+δ ceramics substituted by Y and Zn for Ca and Cu sites, respectively. X-ray diffraction patterns show an incommensurate modulated structure along the b-axis. The structural refinements were carried out using the four-dimensional space group Bbmb(0β1)0 0 0. From the X-ray peak profiles analysis, an anisotropic line-shape broadening was observed. The use of the “Williamson and Hall” method allows distinguishing the origin of broadening as mainly due to microstrains. A large transition from a metallic to semiconductor behaviour is observed on the resistivity curves at x≈0.4 for Bi₂Sr₂Ca_1−xY_xCu₂O_8+δ and at x^′≈0.36 for Bi₂Sr₂Ca_1−xY_xCu_1.94Zn_0.06O_8+δ, which can be also correlated to the defects. Oppositely to the metallic behaviour, which satisfies the Mathiessen's rule, the semiconducting one can be modelled by a variable range hopping process.     

Synthesis and structural analysis of Bi2−ySryIr2O7, a new pyrochlore solid solution

This paper presents a study of the synthesis and structural properties of the new pyrochlore-type Bi_2−ySr_yIr₂O₇ series. Ten compositions with 0.0≤y≤0.9 were prepared by solid-state reaction with thermal treatments at 873, 1073 and 1323 K under atmospheric pressure conditions. Structural refinements from X-ray powder diffraction data by the Rietveld method show that all compounds of the Bi_2−ySr_yIr₂O₇ solid solution crystallize in a α-pyrochlore structure. The main structural difference when bismuth is substituted by strontium concerns the x position of the O1 (x, ?, ?). This substitution significantly increases the Bi/Sr-O1 distance and diminishes the Ir-O1 distance; this implies that the Ir-O1-Ir bond angle increases. With the Sr substitution, the IrO₆ local configuration goes from a flattened trigonal antiprism, y<0.5, to an elongated one, y>0.5, passing through an octahedral array, y∼0.5. The electrical consequences of these structural changes observed in this system are qualitatively explained with electronic structure calculations, this behavior agrees very well with those observed in other pyrochlore systems A₂M₂O₇ (A=rare earth cations or Tl⁺, Pb²⁺, or Bi³⁺, and M=Ru or Ir).     

UV absorption properties of ceria-modified compositions within the fluorite-type solid solution CeO2-Y6WO12

A new fluorite-type solid solution domain has been evidenced in the system (1−x) CeO₂−x/7 Y₆WO₁₂□₂ using the amorphous citrate route. All the studied phases (0?x?1) crystallize in a cubic-type symmetry. Diffuse reflectance spectra reveal a strong optical absorption between 380 and 400 nm. All substituted compositions spectral selectivities are estimated suitable for application as inorganic UV absorbers. The non linear variation observed in the optical gap values between Y₆WO₁₂ and CeO₂ is attributed to the presence of the cerium 4f-block band. Additionally, Time Resolved Microwave Conductivity (TRMC) experiment and phenol photodegradation analyses carried out on the Ce_0.81Y_0.16W_0.03O_1.95□_0.05 (x=0.19) composition do not indicate any photocalatytic activity for this material.     

A novel family of layered bismuth compounds II: the crystal structures of Pb0.6Bi1.4Rb0.6O2Z2, Z=Cl, Br, and I

Using various synthetic approaches, we have prepared over 50 new multinary bismuth oxyhalides which crystallize in four layered structure types. Most of the compounds belong to the three previously reported structure types involving fluorite- and CsCl-like metal-oxygen vs. metal-halogen layers as well as single or double halide ion sheets. The majority of Bi_2−xA_xQ_0.6O₂Z₂ (A=Li, Na, K, Ca, Sr, Ba, Pb; Q=Rb, Cs; Z=Cl, Br, I) compounds crystallize in the tetragonal structure of Pb_0.6Bi_1.4Cs_0.6O₂Cl₂ (Y2) while both Bi_1.4Ba_0.6Q_0.6O₂I₂ (Q=Rb, Cs) oxyiodides adopt its orthorhombically distorted, partially ordered version. Due to the lower degree of substitution, the fluorite-like layers in the Y2 structure accommodate more A cations than previously known for related Bi compounds. However, very large Tl⁺ or Rb⁺ give compounds with another, as yet unknown, structure. We discuss the influence of size and charge of A cations and stoichiometry of [Bi_2−xA_xO₂] fluorite layers on structure and stability of layered oxyhalides of bismuth. Also, we predict formation of isostructural compounds with smaller Q cations like Tl⁺ and K⁺.     

Evolution and characterization of fluorite-like nano-SrBi2Nb2O9 phase in the SrO-Bi2O3-Nb2O5-Li2B4O7 glass system

Transparent glasses of various compositions in the system (100−x)Li₂B₄O₇−x(SrO-Bi₂O₃-Nb₂O₅) (where x=10, 20, 30, 40, 50 and 60, in molar ratio) were fabricated via splat quenching technique. The glassy nature of the as-quenched samples was established by differential thermal analyses. X-ray powder diffraction (XRD) and transmission electron microscopic studies confirmed the amorphous nature of the as-quenched and crystallinity in the heat-treated samples. Fluorite phase formation prior to the perovskite SrBi₂Nb₂O₉ phase was analyzed by both the XRD and high-resolution transmission electron microscopy. Dielectric and the optical properties (transmission, optical band gap and Urbach energy) of these samples have been found to be compositional dependent. Refractive index was measured and compared with the values predicted by Wemple-Didomemenico and Gladstone-Dale relations. The glass nanocomposites comprising nanometer-sized crystallites of fluorite phase were found to be nonlinear optic active.     

Structural and magnetic characterisation of Aurivillius material Bi2Sr2Nb2.5Fe0.5O12

The n=3 Aurivillius material Bi₂Sr₂Nb_2.5Fe_0.5O₁₂ is investigated and combined structural refinements using neutron powder diffraction (NPD) and X-ray powder diffraction data (XRPD) data reveal that the material adopts a disordered, tetragonal (I4/mmm) structure at temperatures down to 2 K. Significant ordering of Fe³⁺ and Nb⁵⁺ over the two B sites is observed and possible driving forces for this ordering are discussed. Some disorder of Sr²⁺ and Bi³⁺ over the M and A sites is found and is consistent with relieving strain due to size mismatch. Highly anisotropic thermal parameters for some oxygen sites suggest that the local structure may be slightly distorted with some rotation of the octahedra. Magnetic measurements show that the material behaves as a Curie-Weiss paramagnet in the temperature range studied with no evidence of any long-range magnetic interactions. Solid solutions including Bi_3−xSr_xNb₂FeO₁₂, Bi₂Sr_2−xLa_xNb₂FeO₁₂ and Bi₂Sr₂Nb_3−xFe_xO₁₂ were investigated but single-phase materials were only successfully synthesised for a narrow composition range in the Bi₂Sr₂Nb_3−xFe_xO₁₂ system.     

Powder preparation and UV absorption properties of selected compositions in the CeO2-Y2O3 system

Several approaches have been investigated to prepare fluorite-type compositions within the (1−x) CeO₂-xYO_1.5 system. The optical properties of the resulting modified-ceria materials have been characterized in order to evaluate their potential abilities as inorganic UV absorbers. Diffuse reflectance analyses reveal a strong optical absorption between 390 and 400 nm for all substituted compositions and the spectral selectivities are estimated suitable for the targeted application. Additionally, time resolved microwave conductivity (TRMC) and phenol photodegradation analyses do not indicate any photocalatytic activity for these compositions. Aqueous colloidal suspensions of the Ce_0.7Y_0.3O_1.85 UV absorber have been carried out.     

Phase relations in NaxCrxTi8−xO16 at 1350 °C and crystal structure of hollandite-like Na2Cr2Ti6O16

Phase relations of rutile, freudenbergite, and hollandite structures were examined in the pseudobinary system NaCrO₂-TiO₂ (i.e., Na_xCr_xTi_8−xO₁₆) at 1350 °C. The hollandite structure was obtained in the composition range 1.7?x?2.0. The symmetry of the samples at room temperature was tetragonal for x=1.7 and 1.75, and monoclinic for x=1.8 and above. Single crystals of monoclinic hollandite Na₂Cr₂Ti₆O₁₆ were grown and the structure refinement has been carried out using an X-ray diffraction technique. The space group was I2/m and cell parameters were a=10.2385(11), b=2.9559(9), c=9.9097(11)Å, and β=90.545(9)° with Z=1. The Na ion distribution in the tunnel was markedly deformed from that in the tetragonal form. It was suggested that Cr/Ti ratios were different between the two framework metal sites.