Synthesis,crystal structure and pseudocapacitor electrode properties of γ-Bi2MoO6 nanoplates

Nanoplate-like bismuth molybdates (γ-Bi₂MoO₆) is prepared for the first time by urea assisted solution combustion synthesis (SCS) and studied the structural and electrochemical properties to explore the possibility of using as negative electrodes in pseudocapacitors. The formation of single phase γ-Bi₂MoO₆ and plate-like morphology is revealed from XRD Rietveld refinement and FESEM, respectively. The pseudocapacitive behaviour of γ-Bi₂MoO₆ is analyzed by cyclic voltammetry and galvanostatic charge–discharge techniques. The effect of Na based aqueous electrolytes on capacitance of the Aurvillius type structured Bi₂MoO₆ is investigated. As prepared γ-Bi₂MoO₆ nanoplates provide the high specific capacitance (519 F g⁻¹) compared with the high-temperature monoclinic phase γ(H) Bi₂MoO₆ in 1 M NaOH electrolyte. The obtained high specific capacitance of as prepared Bi₂MoO₆ could be attributed to the decrease in particle size, increase in active sites, and nanoplate-like structure of as prepared γ-Bi₂MoO₆.     

Synthesis and structure of a new halophosphate Sr3P3O10Cl with the flexible [P3O10]5− anions

A new halophosphate crystal Sr₃P₃O₁₀Cl was grown in molten chloride flux media. It crystallizes in the centrosymmetric orthorhombic space group Pnma (No. 62) with a = 10.617(2) Å, b = 10.736(2) Å, and c = 8.7354(17) Å. In the structure, the basic building unit is the [P₃O₁₀]⁵⁻ anion, which is consist of three PO₄ tetrahedra by sharing the corner oxygen atoms. The two Sr atoms and the Cl atom are linked to construct an infinite [Sr₃Cl]⁵⁺ chain. The [P₃O₁₀]⁵⁻ anions are interconnected with the [Sr₃Cl]⁵⁺ chains to form a three-dimensional frameworks. Additionally, the first-principle calculation was employed to obtain the band structures and densities of states.     

Elucidating the structure of surface acid sites on γ-Al2O3

Differential pair distribution function analysis was applied to resolve, with crystallographic detail, the structure of catalytic sites on the surface of nanoscale γ-Al(2)O(3). The structure was determined for a basic probe molecule, monomethylamine (MMA), bound at the minority Lewis acid sites. These active sites were found to be five-coordinate, forming distorted octahedra upon MMA binding. This approach could be applied to study the interaction of molecules at surfaces in dye-sensitized solar cells, nanoparticles, sensors, materials for waste remediation, and catalysts.     

Synthesis and biological evaluation of potential new inhibitors of the bacterial transferase MraY with a β-ketophosphonate structure

Stable analogs of bacterial transferase MraY substrate or product with a pyrophosphate surrogate in their structure are described. β-ketophosphonates were designed as pyrophosphate bioisosteres and were investigated as UDP-GlcNAc mimics. The developed strategy allows introduction of structural diversity at a late stage of the synthesis. The biological activity of the synthesized compounds was evaluated on the MraY enzyme.     

The structure of the lithium-inserted metal oxide δLiV2O5

Employing neutron and X-ray powder diffraction analysis we have found that the compound at composition LiV₂O₅ formed at ambient temperature on insertion of Li into V₂O₅ has a structure which has been significantly altered from that of the original V₂O₅. The V₂O₅ host acts as a layered compound at high lithium contents: weak VO bonds are broken and neighboring layers both shift and buckle to accommodate the inserted lithium ions. The inserted Li ions are in tetrahedral coordination with oxygen.     

Reaction products and kinetics of the reaction of NO2 with γ-Fe2O3

The reaction of NO(2) with Fe(2)O(3) has relevance for both atmospheric chemistry and catalysis. Most studies have focused on hematite, α-Fe(2)O(3), as it is the thermodynamic stable state of iron oxide; however, other forms of Fe(2)O(3) naturally occur and may have different chemistries. In this study, we have investigated the reaction products and kinetics for NO(2) reacting with γ-Fe(2)O(3) powder using diffuse reflectance infrared Fourier transform spectroscopy and compared the results to those of previous studies of NO(2) reacting with α-Fe(2)O(3). Both α- and γ-Fe(2)O(3) produce surface-bound nitrate at the pressures examined in this study (24-212 mTorr); surface-bound nitrite products are observed at all pressures for γ-Fe(2)O(3) whereas nitrite was only observed on α-Fe(2)O(3) at lower pressures. Surface-bound NO(+) and Fe-NO products are observed on γ-Fe(2)O(3), which have not been observed with α-Fe(2)O(3). The reaction kinetics show a first-order dependence on NO(2) pressure and this is used to support the hypothesis of unimolecular reaction of adsorbed NO(2) with the γ-Fe(2)O(3) surface as the slow step in the reaction mechanism. The difference in product formation between NO(2) reacting with γ-Fe(2)O(3) and previous studies of α-Fe(2)O(3) illustrate the fact that care must be taken in generalizing reactivity of different polymorphs.     

Kinetics of the Thermal Desorption of Atomic Oxygen during Transformations BiO2 – x→ β-Bi2O3→ α-Bi2O3

The thermal desorption of atomic oxygen during the transformations BiO_{2 – x} -Bi₂O₃ -Bi₂O₃is shown to be due to the removal of overstoichiometric oxygen from the bulk of -Bi₂O₃. Oxygen formed at the first stage is desorbed in a molecular form. The maximum desorption rate of atomic oxygen is found before the phase transformation -Bi₂O₃ -Bi₂O₃. The activation energy of the diffusion of excess oxygen in the -Bi₂O₃lattice is 30 kcal/mol.     

Structural and dynamical studies of δ-Bi2O3 oxide ion conductors: I. The structure of (Bi2O3)1−x(Y2O3)x as a function of x and temperature

We report the results of both Bragg and diffuse neutron scattering studies of the superionic solid solution, (Bi₂O₃)_1−x(Y₂O₃)_x. The Bragg data for polycrystalline samples show that the strutural features observed previously in (Bi₂O₃)_0.73(Y₂O₃)_0.27 are present across the entire range of the solid solution, 0.25 < x < 0.42. The number of 〈111〉-displaced anions in the defect fluorite structure decreases with increasing Y³⁺ content whereas the extent of short-range ordering on the anion sublattice increases. Both of these observations are consistent with the decrease in oxide ion conductivity which occurs as x increases. The basic crystal structure does not change between room temperature and 1023 K, although the unit cell volume increases by 3.78% for x = 0.27, and the number of 〈111〉-displaced anions increases, again consistent with the enhanced conductivity observed at high temperatures. It is suggested that Y³⁺ stabilizes the fluorite structure by ordering the vacancies on the oxygen sublattice in chains along the 〈111〉 and 〈110〉 directions.     

TG Study of the Dispersion Threshold of Mn2O3 on γ-Al2O3

Mn₂O₃/-Al₂O₃ catalysts were prepared by the impregnation method, and the maximum monolayer dispersion capacity or dispersion threshold value of Mn₂O₃ on the surface of -Al₂O₃ was determined to be 13.08% from the decomposition mass loss of supported Mn(NO₃)₂ in the monolayer state. This was compared with the values estimated from a close-packed monolayer model and an interaction model. It was confirmed that the high activities and selectivities of the catalysts for benzoic acid hydrogenation to benzaldehyde are due to the monolayer dispersion of the Mn₂O₃ on the surface of -Al₂O₃.This revised version was published online in November 2005 with corrections to the Cover Date.     

Synthesis and selected properties of a new solid solution in the Zn2FeV3O11–Mg2FeV3O11 system

The binary Zn₂FeV₃O₁₁?CMg₂FeV₃O₁₁ system has been studied by XRD, DTA, IR, and SEM methods. A new continuous substitution solid solution with the formula Zn_2?x Mg _x FeV₃O₁₁ has been obtained by high-temperature synthesis. The DTA investigations were used to choose the heating temperatures as well as for determination of thermal stability of the new triclinic phase. The influence of the degree of Mg²⁺ ion incorporation on the unit cell volume as well as on the position of the IR absorption bands of the solid solution have been determined. The morphology of crystals of the new phase is presented.     

Synthesis,structure and reactivity of complexes containing a transition metal–bismuth bond

The transition metal chemistry of bismuth has attracted significant interest since the 1970s. The low cost and high abundance of bismuth(III) reagents, such as the trihalides, makes them ideal starting materials and the size of the bismuth centre allows three- and higher-coordinate complexes to be synthesised, in which the bismuth atom is linked to one or more transition metal fragments. The ability to vary these metal fragments gives access to a plethora of available structures, with cyclopentadienylcarbonyl, metal carbonyl and sandwich compounds of bismuth in existence. Significant recent study has focused on applications in catalysis, where bismuth species can act as cross-coupling agents in carbon–carbon, carbon–nitrogen and carbon–oxygen bond forming reactions. Another striking feature is the variation in bonding situations that can be observed when studying the organometallic chemistry of bismuth. For example, dative and covalent interactions have been reported, in addition to cases of dibismuth acting as a two-, four- or six-electron donating ligand. This review aims to demonstrate the multi-faceted nature of the transition metal chemistry of bismuth and provide a detailed coverage of this topic.     

Synthesis,characterization and magnetic properties of γ-Fe2O3 nanoparticles via a non-aqueous medium

Acicular shaped γ-Fe₂O₃ nanoparticles (major axis: 17±2 nm; minor axis: 1.7±1 nm) have been prepared using lauric acid as a non-aqueous medium. The products were investigated by IR, TG-DTA, XRD, Raman, SEM, TEM and magnetization measurements. For the preparation of pure γ-Fe₂O₃ nanoparticles, the suitable condition of the molar ratio of lauric acid to iron nitrate is set 2:1 and the appropriate temperature lies in the range 573–673 K. Besides, either pure α-Fe₂O₃ or a mixture of γ-Fe₂O₃ and α-Fe₂O₃ can also be obtained with the change of the molar ratio of lauric acid to iron nitrate. The experimental results indicate that the particle sizes, thermal stability and magnetic properties of the iron oxide strongly depend on the conditions in the preparation.     

Crystal structure determination of α, β and γ-Bi4V2O11 polymorphs. Part I: γ and β-Bi4V2O11

Using combined X-ray single crystal and neutron powder thermodiffraction data, the crystal structure of the high temperature γ-form of Bi₄V₂O₁₁ was confirmed and accurately refined in the I4/mmm space group and that of the β-form was entirely determined in the centrosymmetric Amam space group. The two-fold superlattice characterising the β structure is the result of an ordering process involving corner-sharing V–O tetrahedra and disordered trigonal bipyramids. A possible scheme for the γ↔β phase transition is proposed.     

Hydrothermal synthesis and electrochemistry of a manganese vanadium oxide, γ-MnV2O5

A new manganese vanadium oxide MnV₂O₅ has been synthesized using a mild hydrothermal reaction. MnV₂O₅ crystallizes in the orthorhombic system, space group Pnma, a=9.7585(2) Å, b=3.5825(1) Å, c=11.2653(2) Å. It is isostructural to γ-LiV₂O₅. It reacts readily and reversibly with lithium, with a stable capacity but with a large polarization.     

Chemical Modification of γ-Al2O3 Surface with Aryl Silanes

The effect of main factors (the nature and functionality of a modifier, the presence of water) on the chemical modification of -Al₂O₃ surface with aryl silanes was studied by an FTIR spectroscopy and elemental analysis.     

Synthesis of a new aza-14-crown-4 with di(α-pyridyl)-substituted bispidine subunit and the crystal structure of its complex with CoCl2

The aza-14-crown-4 with the di(α-pyridyl)-substituted bispidine subunit (L) and its cationanion complex with cobalt(II) chloride of composition [Co(L)(H₂O)][CoCl₄] (I) have been synthesized. The structure of compound L has been proved by IR spectroscopy, NMR, and mass spectrometry. X-ray crystallography has demonstrated that the L molecule in the complex is an NNNN-tetradentate chelating ligand, and the crown ether moiety is not directly bound to the metal cation. In the cationic moiety of the complex, the Co(1) atom has an octahedral environment, and the Co(2) polyhedron in the anionic moiety is a tetrahedron. The cationic and anionic moieties of complex I are linked by the bridging chlorine atom.