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.

The role of the sp2:sp3 substrate content in carbon supported nanotube growth

We report the growth of vertically-aligned nanotube forests, of up to 0.2 mm in height, on an 85:15 sp2:sp3 carbon support with Fe catalyst. This is achieved by purely-thermal chemical vapour deposition with the catalyst pretreated in inert environments. Pretreating the catalyst in a reducing atmosphere causes catalyst diffusion into the support and the growth of defective tubes. Other sp2:sp3 compositions, including graphite, tetrahedral amorphous carbon, and pure diamond, also lead to the growth of defective carbon morphologies. These results pave the way towards controlled growth of forests on carbon fibres. It could give rise to applications in enhanced fuel cell electrodes and better hierarchical carbon fibre-nanotube composites. © 2014 Elsevier Ltd. All rights reserved.

First-principles study of transition metal impurities in Si

By using ab initio electronic structure calculations within density functional theory, we study the structural, electronic, and magnetic properties of Si doped with a transition metal impurity. We consider the transition metals of the 3d series V, Cr, Mn, Fe, Co, and Ni. To get insight into the level filling mechanism and the magnetization saturation, we first investigate the transition metal-Si alloys in the zinc-blende structure. Next, we investigate the doping of bulk Si with a transition metal atom, in which it occupies the substitutional site, the interstitial site with tetrahedral symmetry, and the interstitial site with hexagonal symmetry. It is found that all of these transition metal impurities prefer an interstitial position in Si. Furthermore, we show that it is possible to interpret the electronic and magnetic properties by using a simple level filling picture and a comparison is made to Ge doped with the same transition metal atoms. In order to get insight into the effect of a strained environment, we calculate the formation energy as a function of an applied homogeneous pressure and we show that an applied pressure can stabilize the substitutional position of transition metal impurities in Si. Finally, the energies of the ferromagnetic states are compared to those of the antiferromagnetic states. It is shown that the interstitial site of the Mn dopant helps us to stabilize the nearest neighbor substitutional site to realize the ferromagnetic state. For doping of Si with Cr, a ferrimagnetic behavior is predicted.

Influence of ion energy and deposition temperature on the surface morphology of carbon films deposited by ion beams

Carbon films were deposited by mass-selected ion beam technique with ion energies 50-200eV at a substrate temperature from room temperature to 80 degreesC,. For the energies used, smooth diamond-like carbon films were deposited at room temperature. When the substrate temperature was 600 degreesC,rough graphitic films were produced. But highly oriented carbon tubes were observed when the energies were larger than 140eV at 800 degreesC. They were perpendicular to the surface and parallel to each other. preferred orientation of graphite basic plane was observed by high-resolution electron microscopy. Shallow ion implantation and stress are responsible for this orientation.

Tentative analysis of Swirl defects in silicon crystals

Swirl defects in dislocation-free Czochralski (CZ) silicon crystals have been investigated by preferential etching, transmission electron microscopy (TER I) and electron energy loss spectroscopy (EELS) mode of a scanning transmission electron microscope (STEM). Two kinds of Swirl defects have been found with a good correspondence between striated pattern consisting of hillocks and the buried micro-defects. The Swirl defects were identified as perfect dislocation loop cluster and tetrahedral precipitate, respectively. In addition, a kind of tiny micro-defects is found to be distributed preferentially in the vicinity of the Swirl pattern although there is no detectable correspondence between hillocks and the micro-defects. The energy-filtered images have been obtained by the plasma peaks at different parts of a coherent precipitate with the Si matrix. The experimental results show some indications of the existence of oxygen and carbon in the core of the precipitate and suggest that oxygen and carbon may play important roles in the formation of Swirl defect. (C) 2000 Elsevier Science B.V. All rights reserved.

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.

On the nature of iron in InP: A FTIR study

Fe is still the commonly used dopant to fabricate semi-insulating(SI) InP, a key material for high-speed electronic and optoelectronic devices. High resolved absorption spectra of the internal d-d shell transitions at Fe2+ in InP and the related phonon sidebands and a series of iron related absorption Lines are presented. Detailed infrared absorption study of the characteristic spectra of four zero-phonon lines(ZPLs), which are attributed to transitions within the 5D ground state of Fe2+ (3d(6)) on the indium site in a tetrahedral crystal field of phosphorus atoms and their temperature effects are given.

Effect of acidity in TS-1 zeolites on product distribution of the styrene oxidation reaction

The role of Bronsted acidity of titanium silicalite zeolite (with different ratios of Si/Ti) in oxidation reactions of styrene has been investigated and discussed. For zeolites with Si/Ti > 42, most of the titanium is in the zeolite framework. These framework titanium species, which act both as the isolated titanium centers and as Bronsted acidity centers (together with the Bronsted acidity produced by the tetrahedral aluminum impurity introduced during synthesis), can catalyze both the epoxidation and the succeeding rearrangement reactions, thus promoting the formation of phenylacetaldehyde. With an increase in the titanium content of the zeolite, titanium will tend to stay outside the zeolite lattice, except for the TiOx nanophases which can be occluded in the zeolite channels or on the external surface. These non-framework titanium species are favorable for the carbon-carbon bond scission, leading to the production of additional benzaldehyde. The catalytic performances of these zeolites with different Si/Ti ratios are correlated here with their structural information by using solid-state NMR and UV-Vis methods. (C) 2003 Elsevier B.V. All rights reserved.

Solid-state MAS NMR studies on the hydrothermal stability of the zeolite catalysts for residual oil selective catalytic cracking

By using the solid-state MAS NMR technique, the hydrothermal stabilities (under 100% steam at 1073 K) of HZSM-5 zeolites modified by lanthanum and phosphorus have been studied. They are excellent zeolite catalysts for residual oil selective catalytic cracking (RSCC) processes. It was indicated that the introduction of phosphorus to the zeolite via impregnation with orthophosphoric acid led to dealumination as well as formation of different Al species, which were well distinguished by Al-27 3Q MAS NMR. Meanwhile, the hydrothermal stabilities of the zeolites (P/HZSM-5, La-P/HZSM-5) were enhanced even after the samples were treated under severe conditions for a prolonged time. It was found that the Si-O-Al bonds were broken under hydrothermal conditions, while at the same time the phosphorous compounds would occupy the silicon sites to form (SiO)(x)Al(OP)(4 - x) species. With increasing time, more silicon sites around the tetrahedral coordinated Al in the lattice can be replaced till the aluminum is completely expelled from the framework. The existence of lanthanum can partially restrict the breaking of the Si-O-Al bonds and the replacement of the silicon sites by phosphorus, thus preventing dealumination under hydrothermal conditions. This was also proved by P-31 MAS NMR spectra. (C) 2004 Elsevier Inc. All rights reserved.

1,1 '-dimethyl-4,4 '-(propane-1,3-diyl)-dipyridinium tetrabromidocadmate(II)

In the cation of the title compound, (C15H20N2)[CdBr4], the dihedral angle between the two pyridine rings is 70.85 (5)degrees. An intermolecular pi-pi interaction between the pyridine rings [centroid - centroid distance = 3.900 (4) angstrom] is observed. The Cd-II atom has a distorted tetrahedral coordination.

Fabrication and Luminescence Properties of One-Dimensional CaMoO4: Ln(3+) (Ln = Eu, Tb, Dy) Nanofibers via Electrospinning Process

One-dimensional CaMoo(4):Ln(3+) (Ln = Eu, Tb, Dy) nanofibers have been prepared by a combination method of sol-gel and electrospinning process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), photoluminescence (PL), and low voltage cathodoluminescence (CL) as well as kinetic decays were used to characterize the resulting samples. SEM and TEM analyses indicate that the obtained precursor fibers have a uniform size, and the as-formed CaMoO4:Ln(3+) nanofibers consist of nanoparticles. Under ultraviolet excitation, the CaMoO4 samples exhibit a blue-green emission band with a maximum at 500 nm originating from the MoO42- groups. Due to an efficient energy transfer from molybdate groups to dopants, CaMoO4:Ln(3+) phosphors show their strong characteristic emission under ultraviolet excitation and low-voltage electron beam excitation.

Uniform AMoO(4):Ln (A = Sr2+, Ba2+; Ln = Eu3+, Tb3+) submicron particles: Solvothermal synthesis and luminescent properties

Rare-earth ions (Eu3+, Tb3+) doped AMoO(4) (A = Sr, Ba) particles with uniform morphologies were successfully prepared through a facile solvothermal process using ethylene glycol (EG) as protecting agent. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), Fourier transform infrared spectroscopy (FT-IR), photoluminescence (PL) spectra and the kinetic decays were performed to characterize these samples. The XRD results reveal that all the doped samples are of high purity and crystallinity and assigned to the tetragonal scheelite-type structure of the AMoO(4) phase. It has been shown that the as-synthesized SrMoO4:Ln and BaMoO4:Ln samples show respective uniform pea nut-like and oval morphologies with narrowsize distribution. The possible growth process of the AMoO(4):Ln has been investigated in detail. The EG/H2O volume ratio, reaction temperature and time have obvious effect on themorphologies and sizes of the as-synthesized products.

Growth of highly crystalline CaMoO4 : Tb3+ phosphor layers on spherical SiO2 particles via sol-gel process: Structural characterization and luminescent properties

Highly crystalline CaMoO4:Tb3+ phosphor layers were grown on monodisperse SiO2 particles through a simple sol-gel method, resulting in formation of core-shell structured SiO2@CaMoO4:Tb3+ submicrospheres. The resulting SiO2@CaMoO4: Tb3+ core-shell particles were fully characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectra (EDS), transmission electron microscopy (TEM), photoluminescence (PL), low-voltage cathodoluminescence (CL), and kinetic decays. The XRD results demonstrate that the CaMoO4:Tb3+ layers begin to crystallize on the SiO2 spheres after annealing at 400 degrees C and the crystallinity increases with raising the annealing temperature. SEM and TEM analysis indicates that the obtained submicrospheres have a uniform size distribution and obvious core-shell structure. SiO2@CaMoO4:Tb3+ submicrospheres show strong green emission under short ultraviolet (260 nm) and low-voltage electron beam (1-3 kV) excitation, and the emission spectra are dominated by a D-5(4) -F-7(5) transition of Tb3+(544 nm, green) from the CaMoO4:Tb3+ shells.

Achiral lanthanide alkyl complexes bearing N,O multidentate ligands. Synthesis and catalysis of highly heteroselective ring-opening polymerization of rac-lactide

Alkane elimination reactions of amino-amino-bis(phenols) H2L1-4, Salan H2L5, and methoxy-beta-diimines HL6,7 with lanthanide tris(alkyl) s, Ln(CH2SiMe3)(3)(THF)(2) (Ln = Y, Lu), respectively, afforded a series of lanthanide alkyl complexes 1-8 with the release of tetramethylsilane. Complexes 1-6 are THF-solvated mono( alkyl) s stabilized by O, N, N, O-tetradentate ligands. Complexes 1-3 and 5 adopt twisted octahedral geometry, whereas 4 contains a tetragonal bipyramidal core. Bearing a monoanionic moiety L-6 (L-7), complex 7 ( 8) is a THF-free bis(alkyl). In complex 7, the O, N, N-tridentate ligand combined with two alkyl species forms a tetrahedral coordination core. Complexes 1, 2, and 3 displayed modest activity but high stereoselectivity for the polymerization of rac-lactide to give heterotactic polylactide with the racemic enchainment of monomer units P-r ranging from 0.95 to 0.99, the highest value reached to date. Complex 5 exhibited almost the same level of activity albeit with relatively low selectivity. In contrast, dramatic decreases in activity and stereoselectivity were found for complex 4. The Salan yttrium alkyl complex 6 was active but nonselective. Bis(alkyl) complexes 7 and 8 were more active than 1-3 toward polymerization of rac-LA, however, to afford atactic polylactides due to di-active sites. The ligand framework, especially the "bridge" between the two nitrogen atoms, played a significant role in governing the selectivity of the corresponding complexes via changing the geometry of the metal center.

Supramolecular isomerism in zinc hydroxide coordination polymers with pyridine-2,4-dicarboxylic acid: Two polymorphs with centrosymmetric two-dimensional and acentric three-dimensional coordination networks

Reactions of Zn(BF4)(2) and pyridine-2,4-dicarboxylic acid (2,4-pydcH(2)) in the presence of 1,2-bis( 4-pyridyl) ethylene or 1,3-bis(4-pyridyl) propane under hydro(solvo) thermal conditions yielded two polymorphic metal-organic coordination polymers formulated as Zn-2(OH)(2)(2,4-pydc) (1 and 2). Polymorph 1 features a two-dimensional (2-D) layer-like structure that is constructed by 2,4-pydc ligands bridging between the Zn-OH-Zn double-chain units. Each single Zn-OH-Zn chain is composed of mu(2)-OH groups connecting trigonal bipyramidal and tetrahedral Zn centers. Polymorph 2 is a 3-D coordination polymer containing 2-D Zn-OH-Zn sheets that consist of mu(2)- and mu(3)-OH groups and trigonal bipyramidal Zn centers. The sheets are pillared by 2,4-pydc ligands to form an acentric structural architecture. 1 and 2 are rare examples that the two polymorphs exhibit a centrosymmetric 2-D coordination network and an acentric 3-D coordination network, respectively. The different structures lead to differences in photoluminescent properties and thermal stabilities for 1 and 2.