The system Ag2Se-Ho2Se3 in the 0-50 mol.% Ho2Se3 range and the crystal structure of two polymorphic forms of AgHoSe2

The phase diagram of the Ag₂Se-Ho₂Se₃ system in the range of 0-50 mol.% Ho₂Se₃ was constructed with the results of XRD and differential thermal analysis. A dimorphous compound exists in the system at the equimolar ratio of the components. The investigated part of the Ag₂Se-AgHoSe₂ diagram is of the eutectic type with the eutectic coordinates 7 mol.% Ho₂Se₃ and 1125 K. The crystal structure of the high-temperature modification of AgHoSe₂ was studied by X-ray powder diffraction method. α-AgHoSe₂ is described as a NaCl structure (space group ) with the lattice parameter а = 5.7623(3) Å. Atomic parameters were calculated in the isotropic approximation (R_I = 0.0434 and R_Р = 0.0636). The crystal structure of β-AgHoSe₂ was determined by X-ray structure analysis and was refined to R = 0.0487.     

Structural stability and mutual transformations of molybdenum carbide, nitride and phosphide

The structural stability and transformations of Mo carbide, nitride and phosphide were investigated under various atmosphere conditions by X-ray diffraction (XRD). The results indicated that the order of structural stability of these Mo-based compounds was as follows: Mo₂N < Mo₂C < MoP. Both Mo₂C and Mo₂N can be transformed to MoP, whereas the reverse transformations did not occur. Noticeably, compared with those Mo sources containing oxygen, the use of Mo₂C/Mo₂N as Mo-source can produce finely dispersed MoP nanoparticles by the temperature-programmed reaction (TPR) method. The result was probably due to the fact that lower-levels H₂O generated during synthesis process can avoid strong hydrothermal sintering. The influence of formation energy had been considered and was found to relate to the structural stability and transformations of these Mo-based compounds.     

Synthesis of single-crystalline Ce(CO3)(OH) with novel dendrite morphology and their thermal conversion to CeO2

Single-crystalline cerium carbonate hydroxide (Ce(CO₃)(OH)) with dendrite morphologies have been successfully synthesized by hydrothermal method at 150 °C using Ce(NO₃)₃·6H₂O as the cerium source, aqueous carbamide as both an alkaline and carbon source and poly(vinyl pyrrolidone) (PVP) as surfactant. Ceria (CeO₂) with dendrite morphologies have been fabricated by a thermal decomposition-oxidation process at 500 °C for 6 h using single-crystalline Ce(CO₃)(OH) dendrites as the precursor. The dendrite morphologies of Ce(CO₃)(OH) was sustained after thermal decomposition-oxidation to CeO₂. The as-prepared products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), field-emission scanning electron microscopy (FE-SEM), and thermogravimetric analysis (TG).     

Synthesis, structure refinement and characterisation of a new oxyphosphate Mg0.50TiO(PO4)

A new titanium oxyphosphate Mg_0.50TiO(PO₄) has been synthesized and characterized by several physical techniques: X-ray diffraction, ³¹P MAS-NMR, Raman diffusion, infrared absorption and diffuse reflectance spectroscopy. It crystallizes in the monoclinic system with unit cell parameters: a = 7.367(9), b = 7.385(8), c = 7.373(9) Å, β = 120.23(1), with the space group P2₁/c (no. 14), Z = 4. The crystal structure has been refined by the Rietveld method using X-ray powder diffraction. The conventional R indices obtained are R_wp = 0.138, R_p = 0.096 and R_B = 0.0459. The structure of Mg_0.50TiO(PO₄) consists of infinite chains of corner-shared [TiO₆] octahedra parallel to the c-axis, crosslinked by corner-shared [PO₄] tetrahedra. These infinite chains have alternating short (1.74 Å) and long (2.26 Å) TiO bonds and are similar to those found in titanium oxyphosphate M^II_0.50TiO(PO₄) (M²⁺ = Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺). The magnesium atom is located in an antiprism between two [TiO₆] octahedra. ³¹P MAS NMR showed only a single ³¹P resonance line, in a good agreement with the crystal structure. Raman and IR spectra show strong bands respectively at 765 and 815 cm⁻¹, attributed to the vibration of TiOTiO bonds in the infinite chains. The gap due to the Oxygen-Titanium(IV) charge transfer is 3.37 eV.     

Polymorph selection and nanocrystallite rearrangement of calcium carbonate in carboxymethyl chitosan aqueous solution: Thermodynamic and kinetic analysis

In this article, the polymorph selection of calcium carbonate has been successfully achieved in water-soluble carboxymethyl chitosan aqueous solution at different temperatures (25-95 °C). Vaterite is formed in carboxymethyl chitosan solution 25 °C accompanied with trace of calcite, whereas pure aragonite is obtained at 95 °C. Scanning electron microscopy and transmission electron microscopy analyses show that the products are formed from the recrystallization of nanometer crystallites. Thermodynamic and kinetic analyses reveal that the polymorph of calcium carbonate is controlled and selected by kinetics in various temperatures. As a heterogeneous nucleator and stabilizing agent, carboxymethyl chitosan changes the nucleation and growth of calcium carbonate from thermodynamic into kinetic control. Under kinetic limitation, the reaction rate of aragonite increases along with the elevating of temperature and surpasses the rate of vaterite above 327 K.     

Characterization of LiNbO3 nanocrystals prepared via a convenient hydrothermal route

LiNbO₃ nanocrystal was successfully prepared via a simple and convenient hydrothermal route using LiOH and Nb₂O₅ as the reactants. Transmission electron microscopy images shows that the as-prepared sample displays a flake-like shape of 40-100 nm. X-ray diffraction, IR spectrum and Raman spectra of the as-prepared sample indicates that the sample was well crystalline and of high purity.     

Re-examination of the structural properties of solid solutions SrxCa1−xCO3

We have re-examined the evolution of orthorhombic cell parameters as a function of the substitution parameter x in solid solutions Sr_xCa_1−xCO₃ in order to clarify contradictory results found in the literature. Calcium carbonate has been synthesized in the presence of Sr²⁺ ions (Sr/Ca molar ratio ranging from 10⁻² to 1), using experimental conditions that previously allowed us to obtain monophasic aragonite. The precipitates obtained have been analysed using powder X-ray diffractometry (XRD) and inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The powder XRD data confirm the occurrence of purely monophasic strontian-aragonites. Moreover, the cell parameters as well as the substitution parameter x have been refined for 0 < x < 0.5 against powder XRD data through Rietveld refinement. On the other hand, x was deduced from chemical analysis by ICP-AES. The agreement between both techniques is very satisfactory. The evolution of the cell parameters as a function of x is found to be linear within the studied range, this feature being confirmed for the overall domain (0 ≤ x ≤ 1) if one takes into account the cell parameters of aragonite CaCO₃ and strontionite SrCO₃. This result, that is consistent with the existence of continuous solid solutions obeying the Vegard's law in the Sr_xCa_1−xCO₃ system, contradicts previously published assertions.     

Synthesis, structure refinement and characterization of tetrahydrated acid gadolinium diphosphate HGdP2O7·4H2O

Synthesis and single crystal structure are reported for a new gadolinium acid diphosphate tetrahydrate HGdP₂O₇·4H₂O. This salt crystallizes in the monoclinic system, space group P2₁/n, with the following unit-cell parameters: a = 6.6137(2) Å, b = 11.4954(4) Å, c = 11.377(4) Å, β = 87.53(2)° and Z = 4. Its crystal structure was refined to R = 0.0333 using 1783 reflections. The corresponding atomic arrangement can be described as an alternation of corrugated layers of monohydrogendiphosphate groups and GdO₈ polyhedra parallel to the () plane. The cohesion between the different diphosphoric groups is provided by strong hydrogen bonding involving the W4 water molecule.

IR and Raman spectra of HGdP₂O₇·4H₂O confirm the existence of the characteristic bands of diphosphate group in 980–700 cm⁻¹ area. The IR spectrum reveals also the characteristic bands of water molecules vibration (3600–3230 cm⁻¹) and acidic hydrogen ones (2340 cm⁻¹). TG and DTA investigations show that the dehydration of this salt occurs between 79 and 900 °C. It decomposes after dehydration into an amorphous phase. Gadolinium diphosphate Gd₄(P₂O₇)₃ was obtained by heating HGdP₂O₇·4H₂O in a static air furnace at 850 °C for 48 h.     

Synthesis and structures of chloride thiosilicates with lanthanides Ln3Cl[SiS4]2 (Ln = La, Ce, Pr)

Single crystals of Ln₃Cl[SiS₄]₂ (Ln=La, Ce, Pr) were prepared by the reaction of lanthanide metal, sulfur, silicon and chlorine. Data collection was carried out using a STOE imaging plate detector at 293 K. The homologue compounds crystallize in the space group C2/c of the monoclinic system isotypically to Ln₃X[SiS₄]₂ (X=Br, I) and the A-type of the halide oxosilicates Ln₃X[SiO₄]₂ (X=Cl, Br; Ln=La, Ce, Pr) with four formula units in cells of dimensions:

•

La₃Cl[SiS₄]₂: a=1567.2(3) pm, b=777.8(2) pm, c=1101.5(2) pm, β=96.88(2)°

•

Ce₃Cl[SiS₄]₂: a=1559.4(3) pm, b=770.2(2) pm, c=1096.9(2) pm, β=97.07(2)°

•

Pr₃Cl[SiS₄]₂: a=1555.9(3) pm, b=764.2(1) pm, c=1093.2(2) pm, β=97.40(2)°

The corresponding residuals (all data) for the refined structures are 2.28% (La), 2.15% (Ce), and 3.17% (Pr), respectively. In the crystal structures, the chloride ions form chains along [0 0 1] with trigonal coordination by the lanthanide ions.     

The calcium based fullerenoïd Ca33Bi22.7Al48O139.05: An enantiomorphic structure of strontium aluminate

The aluminate Ca₃₃Bi_22.7Al₄₈O_139.05, having an enantiomorphic structure from the first fullerenoid oxide Sr₃₃Bi_24.25Al₄₈O_141.375, has been isolated. The structure, solved by X-ray single crystal diffraction is built up from an aluminate framework made of AlO₄ tetrahedra connected through corners and forming a huge “Al₈₄O₂₁₀” sphere where the Al atoms are disposed like the carbon atoms in the C₈₄ fullerene. Difference between the Ca and Sr-phases lies in the composition and the structure of the [Bi_xO_y] cluster stuffing the aluminate sphere. In the Ca-phase, the cluster formulated “Bi_22.7O_45.05” can be ideally described as built up from BiO₆ octahedra, BiO₄L trigonal bipyramids and BiO₃L tetrahedra. The EDS chemical analyses reveal a large domain of cationic stoichiometry, as observed for the Sr-phase. The high resolution electron microscopy (HREM) images of regular zones are in good agreement with the images calculated from the single crystal structure.     

Influence of pH on the sorption behaviour of uranyl ions in mesoporous MCM-41 and MCM-48 molecular sieves

The sorption of uranyl ions in mesoporous MCM-41 and MCM-48 was accomplished with the help of a direct-template-exchange route, and the progress was monitored as a function of pH of the precursor uranyl nitrate solution. Under identical conditions of synthesis, around one and a half times larger amount of uranium was found to be sorbed in MCM-48 (∼12.5 wt.%) as compared to MCM-41 (∼9.5 wt.%). Further, the powder X-ray diffraction (XRD) data revealed that the expansion of unit cell parameters and broadening of reflections of the uranium containing samples depended on the pH of the precursor uranyl solution. Likewise, the Fourier transform infrared spectroscopy (FT-IR) studies showed a progressive decrease in the frequency of the axial OUO asymmetric stretching vibrational band, ν_a(UO) of the anchored uranyl groups with the increase of pH of the exchanging uranyl solution. The presence of two bands at ∼920 and 879 cm⁻¹ for uranyl exchanged samples prepared at pH > 5 indicated the presence of trinuclear (UO₂)₃⁺₅(OH) species. The occlusion of uranium thus depends upon the pore structure of the host material and the nature and dimension of the hydrolysis species formed at a particular pH of uranyl solution. Furthermore, the template-exchange of hexavalent uranium in MCM-41 and MCM-48 not only results in the formation of bulky hydrolysis species in the mesovoids, but also substitutes (isomorphously) in the silicate matrix resulting in the formation of UMCM-41 and UMCM-48.     

Crystal structures and properties of BiMn1−xAlxO3 with x = 0.03 and 0.1

Crystal structures of BiMn_0.97Al_0.03O₃ (I) at 300 and 470 K and BiMn_0.9Al_0.1O₃ (II) at 90 and 300 K were studied with synchrotron X-ray powder diffraction. The strong Jahn-Teller distortion, observed at 300 K in I and associated with orbital order, disappeared at 470 K completely for one site and partially for the second site. The Mn/Al-O distances were very close to each other in I at 470 K and in II at 90 and 300 K indicating that orbital order did not appear in II even at 90 K. Magnetic properties of I and II were investigated with specific heat, high-temperature dc magnetic susceptibility, and ac magnetic susceptibility using different driving ac and applied dc magnetic fields and different ac magnetic field frequencies. The anomaly on the specific heat associated with a magnetic transition was strongly suppressed in II compared with that of I and BiMnO₃.     

Synthesis, crystal structure, and properties of novel perovskite oxychalcogenides, Ca2CuFeO3Ch (Ch = S, Se)

Two new perovskite oxychalcogenides, Ca₂CuFeO₃S and Ca₂CuFeO₃Se, have been synthesized in evacuated quartz tubes. They crystallize in P4/nmm space group with lattice parameters a = 3.8271(1), c = 14.9485(2) Å and a = 3.8605(1), c = 15.3030(2) Å for Ca₂CuFeO₃S and Ca₂CuFeO₃Se, respectively. They appear to be the first layered chalcogenide perovskites involving calcium and are structural analogs of the corresponding Sr and Ba compounds. The new compounds exhibit semiconducting properties with energy gap decreasing from the oxysulfide to the oxyselenide. Possibility of introducing Ca²⁺ into structures of known layered oxychalcogenides and oxypnictides is discussed.     

Structural study and luminescence of TlSrLa(AsO4)2

This work presents the crystal structure and luminescent properties of TlSrLa(AsO₄)₂. In this phase Tl⁺ ions are located in large tunnels delimited by chains of alternating (AsO₄) and (Sr,La)O₈ polyhedra. Thallium atoms are eightfold coordinated with C₁ symmetry. Large TlO distances are observed revealing a low stereochemical activity of the 6s² lone pair. Excitation and emission spectra of Tl⁺ in TlSrLa(AsO₄)₂ showed broad bands at lower energy than those observed in previous works. Excitation spectra are decomposed into multiple Gaussian bands and a theoretical analysis is made to explain the number of observed components. Two Gaussian components are revealed for emission spectra.     

A novel broadband emission phosphor Ca2KMg2V3O12 for white light emitting diodes

A novel broadband emission phosphor Ca₂KMg₂V₃O₁₂ was first synthesized by solution combustion method. The X-ray diffraction showed that Ca₂KMg₂V₃O₁₂ phase can be obtained at 600-900 °C through combustion route. The crystal structure of this material was refined by Rietveld method using powder X-ray diffraction. It crystallizes in cubic system and belongs to space group Ia3d with z = 8, a = 0.12500 nm. The excitation band of Ca₂KMg₂V₃O₁₂ peaks at 320 nm in a region between 260 nm and 425 nm, and the emission spectrum exhibits an intense band centered at about 528 nm covering from 400 nm to 800 nm. The colour coordinates of samples prepared at different ignition temperatures are in a range of x = 0.323-0.339, y = 0.430-0.447.     

Synthesis and crystal structure of Cu2NiO(B2O5) and Cu2MgO(B2O5)

A transport reaction synthesis technique has been used to prepare single crystals of two pyroborate compounds having the formulas Cu₂NiO(B₂O₅) and Cu₂MgO(B₂O₅). The two compounds are isostructural and crystallize in the monoclinic space group P2₁/c. Cu₂NiO(B₂O₅): a=3.2003(10), b=14.775(3), c=9.097(3), β=93.28(4), V=429.4(2) Å³, Z=4; and Cu₂MgO(B₂O₅): a=3.2401(6), b=14.790(2), c=9.147(2), β=94.88(2), V=436.7(2) Å³, Z=4. The structures of Cu₂NiO(B₂O₅) and Cu₂MgO(B₂O₅) were, respectively, refined from 804 and 1000 independent reflections to the final residuals R1=0.0366, wR2=0.0911 and R1=0.0231, wR2=0.0644. Both compounds exhibit a chevron-like structure built up of ribbons, made of edge-connected copper and nickel-oxygen polyhedra, running along the (1 0 0) direction. These ribbons are connected from one another via oxygen atoms and the cohesion of the three-dimensional network is ensured by [B₂O₅] entities. Cu in part occupies the position for Ni or Mg, so that the compounds actually are solid solution compounds. Ni or Mg atoms are octahedrally coordinated by oxygen, while the two pure Cu sites show [4] and [4+1] coordination, for Cu(1) and Cu(2), respectively. The ELNES B-K edge spectra for the two compounds support that the borate group present is [B₂O₅].     

Binary, ternary and quaternary silicates of CaO, BaO and ZnO in high thermal expansion seals for solid oxide fuel cells studied by high-temperature X-ray diffraction (HT-XRD)

Gas-tight seals based on glasses suitable for joining of materials with high thermal expansion coefficients are for example required for solid-oxide fuel cells. If these seals are to be used at high temperatures, they can only be fabricated from glasses which enable the crystallization of phases with high thermal expansion coefficients. This paper reports on some components from systems suitable for high thermal expansion seals: binary calcium silicates, CaSiO₃, Ca₃Si₂O₇ and Ca₂SiO₄ zinc silicates, Zn₂SiO₄, ternary silicates of BaO, CaO and ZnO, BaCa₂Si₃O₉, Ca₂ZnSi₂O₇, and one quaternary silicate, Ba₂CaZn₂Si₆O_17, studied by high-temperature X-ray diffraction. Only CaSiO₃, Ca₃Si₂O₇ and BaCa₂Si₃O₉ exhibit thermal expansion coefficients in the range suitable for high thermal expansion seals of 11.2-11.8 × 10⁻⁶ K⁻¹ (100-800 °C). The thermal expansions strongly depend on the respective crystallographic axis. The coefficient of thermal expansion of a sealing glass is not only affected by the thermal expansions of the crystalline phases, but also by that of the residual glassy phase as well as by the elastic properties. The phase formation should carefully be controlled also with respect to aging.     

Chemical preparation, crystal structure and characterization of the new sodium ytterbium cyclotriphosphate Na3Yb(P3O9)2·9H2O

Chemical preparation and crystal structure are reported for a new lanthanide cyclotriphosphate Na₃Yb(P₃O₉)₂·9H₂O. This salt crystallizes in the trigonal system, space group with the following parameters: a = 30.933(2), c = 12.8282(5) Å. The crystal structure was refined to R₁ = 0.0432 using 1782 reflections with I > 2 σ(I). In the Na₃Yb(P₃O₉)₂·9H₂O structure, the phosphoric ring anions, located around the axis are interconnected by YbO₈ dodecahedra and NaO₆ and NaO₇ polyhedra to build, around the threefold axis, large channels parallel to the c axis. All the nine water molecules in the present arrangement participate in the coordination spheres of the associated cations. The thermogravimetric analysis shows that the removal of these water molecules occurs in three stages between 305 and 736 K.The vibrational study by IR absorption spectroscopy of Na₃Yb(P₃O₉)₂·9H₂O is also reported.     

Crystal structure of rhombohedral MCd(NO2)3 [M = K, Rb, Cs, Tl] from X-ray powder diffraction data

Crystal structure of double nitrites MCd(NO₂)₃ [M=K, Rb, Cs, Tl] at room temperature was ab initio determined from X-ray powder diffraction data. The compounds are isostructural and can be described as rhombohedrally distorted perovskites: space group R3 (no. 146); Z=1; M=K: a=7.5887(1), c=9.1285(2) Å; M=Rb: a=7.6290(1), c=9.2355(2) Å; M=Cs: a=7.7305(1), c=9.4170(3) Å; M=Tl: a=7.6219(1), c=9.2300(2) Å. The coordination polyhedra of cadmium and M cations are the distorted tricapped trigonal prism [(3O+3N)+3O] and cuboctahedron, respectively.     

One-dimensional lone electron pair micelles in the crystal structure of Pb5(SiO4)(VO4)2

The structure of Pb₅(SiO₄)(VO₄)₂ (hexagonal, P6₃/m, a = 9.9865(11), c = 7.3599(12) Å, V = 635.67(14) Å³, Z = 2) has been solved by direct methods and refined to R₁ = 0.051 on the basis of 440 unique observed reflections with |F_o|≥4σ_F. The compound belongs to the apatite structure type. The Pb coordination polyhedra are distorted due to the presence of stereoactive lone electron pairs Ψ. The structure contains channels running along the c axis and centered at (00z). The channels are most probably occupied by the lone electron pairs of the Pb²⁺ cations and thus represent lone electron pair micelles. The existence of such micelles in the structure may well be the reason for the electrogyratory effect and protonic conductivity observed in crystals of the title compound.