M(C6H16N3)2(VO3)4 as heterogeneous catalysts. Study of three new hybrid vanadates of cobalt(II), nickel(II) and copper(II) with 1-(2-aminoethyl)piperazonium.

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Propriedades luminescentes do SrGa2O4 dopado com íons de Ni2+

O objetivo deste trabalho é a síntese e investigação estrutural e óptica de amostras SrGa2O4 dopados com 1% de íons Ni2+. Estas amostras foram sintetizados por reação do estado sólido convencional, utilizando como materiais de partida de alta pureza Ga2O3, SrCO3 e NiO em quantidades estequiométricas. As amostras foram caracterizadas estruturalmente pelo método de difração de raios - X( XRD ) e as medições de difração mostraram que as amostras têm uma única fase monoclínica. Os padrões de XRD também foram refinados pelo método de Rietveld, que permitiu a determinação dos parâmetros de célula unitária. A Caracterização óptica das amostras puras e dopadas SrGa2O4 foram realizadas as medições a partir de fotoluminescência, de excitação e de absorção fotoacústica, à temperatura ambiente. Os espectros de emissão mostraram três bandas de emissão localizadas em 557 nm, 661 nm e 844 nm e foram identificadas essas bandas, respectivamente, com as seguintes transições eletrônicas :1T2 (1D) → 3A2 (3F), 3T1 (3F)→ 3A2 (3F) e 1T2 (1D) → 3T2 (3F). Os espectros de excitação mostraram seis bandas de absorção associadas às transições electrônicas do nível 3A2 (3F) para o 3T1 (3P) , T1 (3P), 1A1 (1G), 1T2 (1D), 3T1 (3F), 1E (1D) e 1T2, 1E (1G). Medidas de absorção fotoacústica também foram realizados com o fim de verificar as transições ópticas observadas nos espectros de excitação e de identificar novas bandas de absorção óptica. Os resultados demonstraram que os íons de Ni2+ ocupam dois locais octaédricos diferentes na amostra SrGa2O4 dopado. A partir das transições ópticas observadas nos espectros de excitação e fotoacústica, determinou-se o parâmetro de cristal de campo, dq, e parâmetros Racah, B e C. A proporção Dq / B ≈ 1.2 para ambos os locais são típicos para Ni2+ íons inseridos em redes de óxido e em coordenação octaédrica.

Propriedades fotoluminescentes e higroscopia do composto SrAl2O4 dopado com íons de Ni2+

Amostras foram preparadas pelo método de difusão a partir dos reagentes químicos SrCO3, Al2O3 e NiO em proporções estequiométricas. Medidas por difração de raios X mostraram que as amostras possuem uma única fase: SrAl2O4. Neste trabalho apresentamos imagens de microscopia eletrônica de varredura das amostras SrAl2O4 dopadas com 0,1%, 0,5%, 1,0%, 2,0%, 5,0% e 10,0% de íons de Ni2+, medidas de fotoluminescência, excitação da fotoluminescência da amostra SrAl2O4 dopada com 1,0% de íons de Ni2+, medidas de absorção fotoacústica das amostras SrAl2O4 dopadas com 1,0%, 2,0%, 5,0% e 10,0% de íons de Ni2+. Estas medidas foram realizadas a temperatura ambiente para investigar as transições eletrônicas dos íons divalente de níquel que entraram substitucionalmente nos sítios de Sr2+ da rede do SrAl2O4. Os resultados ópticos mostram a existência de três centros emissores de Ni2+. De acordo com a literatura, a estrutura do SrAl2O4 é composta de dois sítios octaédrico distintos de íons de Sr2+, o Sr12+ e o Sr22+, cujas distâncias médias Sr1 O e Sr2 O são, respectivamente, 2,800 Ǻ e 2,744 Ǻ. Visto que os íons de Ni2+ tendem a substituir os íons de Sr2+, devido ao fato de possuírem a mesma valência, é necessário considerar que uma parte dos íons de Ni2+ ocuparam os sítios dos íons de Al3+ na rede do SrAl2O4 para justificar a existência de um terceiro centro emissor de Ni2+ nesse composto. Uma novo sítio octaédrico para os íons de Ni2+ foi estimado a partir do valor da aresta do sítio tetraédrico ocupado pelos íons de Al3+ na rede do SrAl2O4 (considerando o raio iônico do Ni2+ como aproximadamente 40% maior do que o raio iônico do Al3+). As transições eletrônicas presentes nos espectros de excitação e absorção fotoacústica permitiram determinar os parâmetros de campo cristalino (Dq) e Racah (B e C) para os três sítios diferentes ocupados pelos íons de Ni2+ no SrAl2O4. Neste caso, os resultados mostraram que o sítio II dos íons de Ni2+ é associado à posição do Sr1 e possuem um parâmetro Dq menor e que o parâmetro Dq associado aos íons de Ni2+ que substituíram os íons de Sr no sitio I, o qual, por sua vez é associado à posição do Sr2. E, por fim, o sítio III que possui o menor parâmetro de campo cristalino Dq, portanto a maior distância íon ligante, é identificado como aquele relacionado ao rearranjo octaédrico local das antigas posições de Al3+. O caráter higroscópico do SrAl2O4:Ni2+ é observado a partir dos espectros de absorção fotoacústica e os modos de vibração de estiramento das ligações Ni OH e O H são identificadas nos espectros.

Wrapping the cube and other polyhedra

An infinite series of twofold, two-way weavings of the cube, corresponding to 'wrappings', or double covers of the cube, is described with the aid of the two-parameter Goldberg- Coxeter construction. The strands of all such wrappings correspond to the central circuits (CCs) of octahedrites (four-regular polyhedral graphs with square and triangular faces), which for the cube necessarily have octahedral symmetry. Removing the symmetry constraint leads to wrappings of other eight-vertex convex polyhedra. Moreover, wrappings of convex polyhedra with fewer vertices can be generated by generalizing from octahedrites to i-hedrites, which additionally include digonal faces. When the strands of a wrapping correspond to the CCs of a four-regular graph that includes faces of size greater than 4, non-convex 'crinkled' wrappings are generated. The various generalizations have implications for activities as diverse as the construction of woven-closed baskets and the manufacture of advanced composite components of complex geometry. © 2012 The Royal Society.

Single sublattice endotaxial phase separation driven by charge frustration in a complex oxide.

Complex transition-metal oxides are important functional materials in areas such as energy and information storage. The cubic ABO3 perovskite is an archetypal example of this class, formed by the occupation of small octahedral B-sites within an AO3 network defined by larger A cations. We show that introduction of chemically mismatched octahedral cations into a cubic perovskite oxide parent phase modifies structure and composition beyond the unit cell length scale on the B sublattice alone. This affords an endotaxial nanocomposite of two cubic perovskite phases with distinct properties. These locally B-site cation-ordered and -disordered phases share a single AO3 network and have enhanced stability against the formation of a competing hexagonal structure over the single-phase parent. Synergic integration of the distinct properties of these phases by the coherent interfaces of the composite produces solid oxide fuel cell cathode performance superior to that expected from the component phases in isolation.

Stabilization of a complex perovskite superstructure under ambient conditions: Influence of cation composition and ordering, and evaluation as an SOFC cathode

Ba1.6Ca2.3Y1.1Fe5O13 is an Fe3+ oxide adopting a complex perovskite superstructure, which is an ordered intergrowth between the Ca2Fe2O5 and YBa2Fe3O8 structures featuring octahedral, square pyramidal, and tetrahedral B sites and three distinct A site environments. The distribution of A site cations was evaluated by combined neutron and X-ray powder diffraction. Consistent with the Fe3+ charge state, the material is an antiferromagnetic insulator with a Néel temperature of 480-485 °C and has a relatively low d.c. conductivity of 2.06 S cm-1 at 700 °C. The observed area specific resistance in symmetrical cell cathodes with the samarium-doped ceria electrolyte is 0.87 Ω cm2 at 700 °C, consistent with the square pyramidal Fe3+ layer favoring oxide ion formation and mobility in the oxygen reduction reaction. Density functional theory calculations reveal factors favoring the observed cation ordering and its influence on the electronic structure, in particular the frontier occupied and unoccupied electronic states. © 2010 American Chemical Society.

Magnetic properties of ZnO-doped cobalt ferrite

The cobalt ferrites with chemical composition Co1+xZnxFe2-2xO4 (r=0.0, 0.1, 0.2, 0.4) were obtained with conventional solid reaction. The ZnO-doped samples have lower lattice constant than CoFe2O4 by adjusting Co ions to the octahedral sites. The results show that doping ZnO could extremely improve the magnetic properties. In comparison with pure CoFe2O4, the little ZnO-doped sample has higher permeability and much lower coercivity at the condition of a little decrease of magnetization saturation. Sample with x=0.1 shows evident magnetostrictive effect at the magnetic field of 30-60 mT while pure cobalt ferrite sample does not, though the saturation magnetostriction decreases. These indicate that ZnO-doping improves the magnetostrictive sensitivity of the cobalt ferrites and have potential applications in magnetoelectric devices and magnetic detector.

Magnetic properties of tin-doped magnetite nanoparticles

Structural and magnetic characteristics of Fe3-xSnxO4 (x < 0.3) nanoparticles synthesized using the precipitation exchange method have been investigated by X-ray diffraction, transmission electron microscope, Mossbauer spectra, X-ray photoelectron spectroscopy and magnetization measurement. The mean particle dimension decreases from 8 to 6 nm, the lattice parameters enlarge, the saturation magnetization decreases, as well as the magnetization and the coercive field increase, with increasing tin-content. The paramagnetic property of the specimens indicates that the replacement of Fe3+ by Sn4+ on the octahedral sites of Fe3O4 causes a progressive lowering of the Curie temperature and the Curie temperatures of the materials are all lower than that of crystallite tin-doped magnetite. This striking debasing is due to the lessening of the grain size. This is the smallest size reported thus far for paramagnetic tin-doped magnetite particles. (c) 2006 Elsevier B.V. All rights reserved.

Magnetic properties of ZnO-doped cobalt ferrite

The cobalt ferrites with chemical composition Co1+xZnxFe2-2xO4 (r=0.0, 0.1, 0.2, 0.4) were obtained with conventional solid reaction. The ZnO-doped samples have lower lattice constant than CoFe2O4 by adjusting Co ions to the octahedral sites. The results show that doping ZnO could extremely improve the magnetic properties. In comparison with pure CoFe2O4, the little ZnO-doped sample has higher permeability and much lower coercivity at the condition of a little decrease of magnetization saturation. Sample with x=0.1 shows evident magnetostrictive effect at the magnetic field of 30-60 mT while pure cobalt ferrite sample does not, though the saturation magnetostriction decreases. These indicate that ZnO-doping improves the magnetostrictive sensitivity of the cobalt ferrites and have potential applications in magnetoelectric devices and magnetic detector.

Effects of point defects on lattice parameters of semiconductors

A model for analyzing the correlation between lattice parameters and point defects in semiconductors has been established. The results of this model for analyzing the substitutes in semiconductors are in accordance with those from Vegard's law and experiments. Based on this model, the lattice strains caused by the antisites, the tetrahedral and octahedral single interstitials, and the interstitial couples are analyzed. The superdilation in lattice parameters of GaAs grown at low temperatures by molecular-beam epitaxy can be interpreted by this model, which is in accordance with the experimental results. This model provides a way of analyzing the stoichiometry in bulk and epitaxial compound semiconductors nondestructively.

Morphology-controlled synthesis of magnetites with nanoporous structures and excellent magnetic properties

Different morphological single-crystal magnetites (Fe3O4) with a nanoporous structure, which exhibit excellent magnetic properties, have been synthesized by a polyol process. Both the type of polyol and the concentration of KOH play important roles in the formation of various morphologies. Cubic, truncated-octahedral, and octahedral shapes can be prepared by changing the concentration of the KOH solution in ethylene glycol.

Synthesis and structure of new low dimensional polymeric haloplumbate(II) complexes [Pb4Br12(C40H40N8)] and [Pb4Cl12(C40H40N8)]center dot H2O

New low dimensional polymeric haloplumbate(II) complexes of the dication of (4,4'-bis(imidazolyl-ylmethyl)biphenyl) were synthesised and their crystal structures determined. Complex 1, [Pb4Br12(C40H40N8)], has cis-edge-shared, octahedral, lead bromide double chains. In compound 2 [Pb4Cl12(C40H40N8)]center dot H2O, the inorganic chains are corner-shared, square pyramidal chains of lead chloride. In both compounds the organic ammoniums form regular layers that alternate with the inorganic chains.

Rare-Earth Metal Bis(alkyl)s Supported by a Quinolinyl Anilido-Imine Ligand: Synthesis and Catalysis on Living Polymerization of epsilon-Caprolactone

The tridentate ligand N-(2-((2,6-diisopropylphenylimino)methyl)phenyl)quinolin-8-amine (HL) was prepared. Treatment of HL with 1 equiv of Ln(CH2SiMe3)(3)(THF)(2) afforded the corresponding rare-earth metal bis(alkyl) complexes LLn(CH2SiMe3)(2)(THF)(n) (Ln = Sc, n = 0 (1); Y, n = 1 (2); Lu, n = 0 (3)) in high yields. Variable-temperature H-1 NMR spectral analysis showed that these complexes were fluxional at room temperature. Complexes 1 and 3 were THF-free, where the metal center adopted a square-pyramidal geometry, while in 2 the metal center generated a distorted octahedral geometry owing to the coordination of a THF molecule.

Morphology control of nanoscale PbS particles in a polyol process

Nanostructured PbS with different morphologies and particle sizes have been prepared through a polyol process. Narrow size distribution for star-shaped, octahedral, tetradecanehedral, and cubic products were achieved by slowly introducing the source materials using a peristaltic pump in the presence of poly(vinylpyrrolidone) (PVP) as additive. Systematic variation of the kinetic factors, including the additive, the reaction temperature, the duration time, the ratio of source materials, the Sulfur sources, and the Pb(Ac)(2)center dot 3H(2)O concentration, reveals that the morphology depends mainly on the supersaturation degree of the free sulfur ions released from thiourea under elevated temperature.

Ethylene Polymerization of the New Titanium Complexes Bearing a Phosphine Oxide-Bridged Bisphenolato Ligand

A series of novel titanium(IV) complexes combining a phosphine oxide-bridged bisphenolato ligand TiCl2{2,2'-O=P-R-3 (4-R-2-6-R-1-C6H2O)(2)}(THF) (6a: R-1 = tBu, R-2 - H, R-3 Ph; 6b: R-1 - Ph, R-2 = H, R-3 = Ph; 6c: R-1 = R-2 = tBu, R-3 = Ph; 6d: R-1 = R-2 cumyl, R-3 = Ph; 6e: R-1 = tBu, R-2 = H, R-3 = PhF5) were prepared by the reaction of corresponding bisphenolato ligands with TiCl4 in THF. X-ray analysis reveals that complex 6a adopts distorted octahedral geometry around the titanium center. These catalysts were performed for ethylene polymerization in the presence of modified methyaluminoxane (MMAO).