ABSTRACT
In the present work, two compounds, in the Bi-Nd-Cr-S and Pb-Nd-Nb-Se systems, not reported to date were synthesized. The chemical composition and the structural determination of these complex compounds, at atomic resolution, was performed through conventional and aberration-corrected electron microscopy including selected area electron diffraction, high resolution (HR) transmission electron microscopy (TEM), HR scanning TEM, and the analytical associated techniques X-ray energy-dispersive spectroscopy and electron energy-loss spectroscopy. The average compositions are [(Bi0.4,Nd0.6)S]1.25CrS2 and [(Pb0.5,Nd0.5)Se]1.15(Nb1.0Se2)2, respectively. By using these electron microscopy techniques, we confirmed that both compounds can be described in term of two interpenetrated sublattices that fit along a but do not fit along b, giving rise to an incommensurate modulation. A closer inspection along the stacking direction of the subcell has provided an ideal structural model for [(Bi0.4,Nd0.6)S]1.25CrS2 based on the intergrowth of one layer of CrS2, three atoms thick, (111) B1 type, and one layer of (Bi, Nd)Se, two atoms thick, (100) B1 type. In [(Pb0.5,Nd0.5)Se]1.15(Nb1.0Se2)2 we found that two layers of NbSe2, which adopt the 2H-NbSe2 polytype, alternate with one layer of (Pb, Nd)Se B1 type. In addition, crystals showing extended defects, associated with the weak interaction between the layers, were frequently found.
ABSTRACT
In the search for the new generation of electrochemical energy storage materials, a novel and straightforward synthetic route for porous carbons and metal oxide nanoparticle composites based on the chlorination of the organometallic compounds Ni(C5H5)2 and Mn(C5H7O2)2 at moderate temperatures, followed by hydrothermal treatment, has been developed. Electrochemical measurements in a three-electrode configuration show that, in both composites NiO@ODC and Mn3O4@ODC, a synergistic effect between the capacitive and pseudocapacitive energy storage mechanisms is observed, thereby improving their electrochemical performance vs pure carbon materials. Electrochemical evaluation of symmetric cells gave gravimetric capacitances of 124 and 130 F g-1 for NiO@ODC and Mn3O4@ODC, respectively. However, the porous structure of the carbon matrix and the higher conductivity of Mn3O4, together, were found to be responsible for the superior electrochemical performance of Mn3O4@ODC.
ABSTRACT
Single crystals of anti-mony-doped germanium, Ge1-x Sb x+0.01 (x ≃ 0.0625), were grown by chemical transport reaction. The alloy crystallizes as a superstructure of diamond-type α-Ge. All atoms in the asymmetric unit lie on special positions and are characterized by strong covalent bonds. The anti-mony atoms substitute for one germanium atom at full occupancy at Wyckoff position 4a (site symmetry -43m), and are also at an adjacent tetra-hedral inter-stitial site with partially occupation (16%) at position 4c (or 4d) (site symmetry -43m). The structural model does not show close Sbâ¯Sb contacts, and suggests that the inter-stitial anti-mony atoms move between the two adjacent tetra-hedral sites.
ABSTRACT
Single crystals of the mercury chalcohalide Hg3-x Sb x (S+Se)2+x I2-x (x ≃ 0.1) (mercury anti-mony sulfide selenide iodide), were grown by a chemical transport reaction. The structure contains three independent A (Hg/Sb) atoms; each atom is strongly covalently bonded with two X (Se/S) atoms to form approximately linear X-A-X units. The X-A-X units link to form A 4 X 4 rings, which are combined into infinite crankshaft-type bands running along the [100] direction. Four equatorial E (I/X = Se,S) atoms at relatively long distances complete the distorted octa-hedral coordination of A (Hg/Sb). The crystal under investigation was twinned by non-merohedry with a refined twin domain fraction of 0.814â (6):0.186â (6). The structure is isotypic with Hg3Se2I2 [Beck & Hedderich (2000 â¸). J. Solid State Chem. 151, 73-76], but the current determination reveals a coupled substitution, with partial replacement of Hg(+2) by Sb(+3), balanced by the equivalent substitution of I(-1) by S(-2) and Se(-2). Bond-valence calculations are consistent with this relative substitution model.
ABSTRACT
Single crystals of octa-deca-nickel dodeca-germanide were grown by chemical transport reaction. The inter-metallic compound crystallizes in a superstructure of the hexa-gonal NiAs type (B8 type). All atoms in the asymmetric unit lie on special positions except one Ni atom (two Ni atoms have site symmetry -6.. and another one has site symmetry .2. while the Ge atoms have site symmetries 32., m.. and 3..). In the structure, the Ni atoms are arranged in 11- or 13-vertex polyhedra (CN = 11-13). The coordination polyhedra of the Ge atoms are bicapped square anti-prisms (CN = 10) or 11-vertex polyhedra (CN = 11). The structure exhibits strong Geâ¯Ni inter-actions, but no close Geâ¯Ge contacts are observed. The Ni atoms with CN = 13 form infinite chains along [001] with an Ni-Ni distance of 2.491â (2)â Å.
ABSTRACT
Single crystals of Cd4As2Br3 (tetra-cadmium biarsenide tri-bromide) were grown by a chemical transport reaction. The structure is isotypic with the members of the cadmium and mercury pnictidohalides family with general formula M 4 A 2 X 3 (M = Cd, Hg; A = P, As, Sb; X = Cl, Br, I) and contains two independent As atoms on special positions with site symmetry -3 and two independent Cd atoms, of which one is on a special position with site symmetry -3. The Cd4As2Br3 structure consists of AsCd4 tetra-hedra sharing vertices with isolated As2Cd6 octa-hedra that contain As-As dumbbells in the centre of the octahedron. The Br atoms are located in the voids of this three-dimensional arrangement and bridge the different polyhedra through Cdâ¯Br contacts.
ABSTRACT
Single crystals of the title compound, octa-iodide deca-anti-monate hexa-tria-conta-germanide, were grown by chemical transport reactions. The structure is isotypic with the analogous clathrates-I. In this structure, the (Ge,Sb)(46) framework consists of statistically occupied Ge and Sb sites that atoms form bonds in a distorted tetra-hedral arrangement. They form polyhedra that are covalently bonded to each other by shared faces. There are two polyhedra of different sizes, viz. a (Ge,Sb)(20) dodeca-hedron and a (Ge,Sb)(24) tetra-cosa-hedron in a 1:3 ratio. The guest atom (iodine) resides inside these polyhedra with symmetry m3 (Wyckoff position 2a) and 2m (Wyckoff position 2d), respectively.
ABSTRACT
Transmission electron microscopy observations on a new complex oxybromide with nominal composition Bi(4)Fe(1/3)W(2/3)O(8)Br, heated at high temperature, reveal the transformation of its basic structure yielding two types of crystals. The first crystal type shows ordered and disordered extended defects leading to a new family of intergrowths between one Sillén block and n Aurivillius blocks and occasionally between one Aurivillius block and n Sillén blocks. The second type presents a compositionally modulated structure, determined by electron diffraction, with an average composition Bi(4)Fe(1/2)W(1/2)O(8 - delta)Br and unit-cell parameters a = (1/gamma) 3.8, b = 3.8, c = 14.5 A (gamma = 0.10-0.15) in the superspace group Immm[(1 - gamma)00] no. 71.1.
