Decomposition of tetraalkylammonium thiotungstates characterized by thermoanalysis, mass spectrometry, X-ray diffractometry and scanning electron microscopy

Thermal decomposition reactions of tetraalkylammonium thiotungstates, (R₄N)₂WS₄ (R = methyl to heptyl), were investigated with DSC and DTA-TG coupled with mass spectroscopy (MS). The results demonstrate that the complexity of thermal decomposition reactions is significantly influenced by the alkyl group, i.e., more complex steps are observed for the materials with longer alkyl chain lengths. Tetraethyl and tetrapropyl complexes show reversible and irreversible phase transitions detected by DSC experiments combined with thermodiffractometry. The tetrapentyl compound undergoes an irreversible phase transition while the tetraheptyl sample exhibits a glass-like transition and melting prior to decomposition. The whole series of compounds decompose without forming sulfur rich WS_n (n = 3 or 4) intermediates. The final WS₂ products are nearly stoichiometric for R = methyl to pentyl but for hexyl and heptyl samples the sulfur content is significantly reduced with a W/S ratio of about 1.5. The residual carbon and hydrogen contents increase in the final decomposition products in the same order as the number of C atoms in R₄N increase. For the N content no clear trend is obvious. A general thermal decomposition mechanism is suggested which follows a bimolecular nucleophilic substitution reaction. In the SEM images only for R = heptyl the formation of macro-pores with a sponge-like morphology is seen, but for the other precursors compact materials are formed which in part display a well developed morphology. X-ray diffraction analysis of the final products shows the formation of amorphous WS₂ up to the tetrapentyl precursor. But for the tetrahexyl and tetraheptyl materials the W:S ratio is significantly smaller than 1:2 and large amounts of C and H are determined by chemical analyses. In accordance with previously reported results it can be assumed that a carbosulfide phase is formed by a mixed C-W-S sandwich layered structure.     

Pilot-plant for NOx, SO2 and HC removal from flue-gas of municipal waste incinerator by electron beam irradiation

According to the basic research performed using a small size reactor at TRCRE of JAERI, the electron beam irradiation process was proved to be very effective for NO_x, SO₂ and HC removals from flue-gas of municipal waste incinerators. Based on this result, a pilot-plant was constructed for the demonstration of NO_x, SO₂ and HC removal performance using electron accelerator of maximum energy 0.95 MeV and maximum power 15kW.The pilot-plant was constructed at Matsudo City waste Disposal Center. The flue-gas of 1,000 Nm³/hr is guided from the waste incinerator flue-gas line of 30,000Nm³/hr to the pilot-plant to be processed by spraying Ca(OH)₂ slurry or powder and irradiation with high-energy electron beam of the accelerator. NO_x, SO₂ and HC are removed simultaneously from the flue-gas by the enhanced reaction with Ca (OH)₂ under irradiation.A brief explanation of the pilot-plant and preliminary results of the experiments are introduced in this paper.     

Characterization of high-temperature superconductors by electron microprobe analysis

In order to optimize the physical properties of HTSC small single crystals grown from a melt for basic studies of their physical properties the influence of the environment on their impurity content was investigated by EPMA. This requires quantitative analysis of all elements being present in the crystals. The accuracy of results was affected by problems with the choice and quality of standards, by contamination but also by malfunction of microprobe electronics. The HTSC materials were found to react with mills, milling balls, crucibles and the atmosphere. These problems are being discussed and some reactions being studied for Y₁Ba₂Cu₃O_6+x (0 < x < 1) HTSC in A1₂O₃ and ZrO₂ crucibles. The crystals grown contain reproducible amounts of impurities depending on boundary conditions and exhibit a zone structure in composition particularly for Y and Ba within their range of homogeneity.     

Structures,stabilities and adiabatic ionization and electron affinity energies of small sulfur clustersS 3-S 5

Summary The vertical and adiabatic ionization and electron affinity energies are calculated for the isomers ofS ₃,S ₄ andS ₅. For the existing isomers the structures of several ionic states were optimized using an RHF analytical gradient approach with a subsequent frequency analysis. The many-body effects were taken into account by Green function (for vertical energies) and CI (for vertical and adiabatic energies) techniques. The structural relaxation upon ionization or attachment of an electron is found to be of primary importance to account for the sequence of cationic states or the existence of a positive electron affinity.Dedicated to Professor W. Kutzelnigg on the occasion of his 60th birthday.     

On the modulation of electron energy distribution function in radiofrequency SiH4, SiH4−H2 bulk plasmas

Electron energy distribution functions (EDF) in SiH₄, SiH₄–H₂ radiofrequency discharges have been calculated by solving the time-dependent Boltzmann equation in the presence of a sinusoidal field. Particular emphasis is given to the modulation of EDF as a function of the applied frequency (·10⁶/p ₀ ·10⁸ sec^–1 torr^–1) and of gas composition. The results show that at /p ₀ = ·10⁶ sec^–1 torr^–1 EDF follows in a quasistationary mode the variation of the field with the exception of a small range of electric field near to the zero crossing. Still, at the higher considered frequency (/p ₀ =·10⁸ sec^–1 torr^–1), we observe some modulation of EDF. The necessity of using a time-dependent approach is tested by comparing the present results with the corresponding ones obtained by using the effective field approximation (i.e., the approximation which solves instead of the time-dependent Boltzmann equation the corresponding stationary one at the effective values of the rf field). The two sets of results can differ by orders of magnitude in the tail of EDF, the differences decreasing with increasing molar fraction of H₂ and increasing field frequency. The role of excited states (second-kind collisions) is studied by inserting in the Boltzmann equation given concentrations of vibrational and electronic states. The results show that second-kind collisions strongly affect EDF especially in pure silane. Finally a satisfactory agreement has been found between theoretical and experimental results concerning the modulation of electrons of given energy in pure silane discharges.     

Exfoliated nanoplatelets of an Aurivillius phase, Bi3.25La0.75Ti3O12: Characterisation by X-ray diffraction and by high-resolution electron microscopy

Nanoparticles of the Aurivillius phase La-substituted BTO (Bi_4−xLa_xTi₃O₁₂, with x=0.75) were obtained through a chemical lithiation process. They have been characterised by X-ray diffraction and transmission electron microscopy (diffraction and imaging at high resolution). The defect-free particles are platelet-shaped with the c large axis perpendicular to the plane. From high-resolution images, it is clear that the delamination process occurs at the level of the (Bi₂O₂)²⁺ intermediate layer and is destructive for this layer. The smallest thickness measured corresponds to one cell parameter (3.3 nm) but a large range of thicknesses have been observed: this suggests that the lithium insertion does not take place in all (Bi₂O₂)²⁺ layers, despite a large excess of lithium and a long reaction time. This is confirmed by ICP analysis, which leads to a formula Li_0.99Bi_3.25La_0.77Ti_3.00O₁₂ for the lithiated compound. This behaviour towards lithium intercalation differs from those observed with BTO in literature, where lithium insertion is reported as occurring in every (Bi₂O₂)²⁺ layer. Possible explanations for this difference are advanced based on microstructural and structural considerations.     

N2O4 complexes with electron donor molecules. An STO-3G study

The quantum chemical calculations for N₂O₄ complexes with some electron-donor molecules: CH₃NO₂, CH₃COOH, CH₃CN, C₆H₆ and with another molecule of N₂O₄ show that the donor molecule lies under the N₂O₄ plane and its electron-donor atom points to the center of N-N bond of N₂O₄ (or near this center). The electron charge is transferred from the donor to N₂O₄ molecule, mostly to the N-N bond of N₂O₄.     

Structure and electron density analysis of electrochemically and chemically delithiated LiCoO2 single crystals

Single crystals of Li_0.68CoO₂, Li_0.48CoO₂, and Li_0.35CoO₂ were successfully synthesized for the first time by means of electrochemical and chemical delithiation processes using LiCoO₂ single crystals as a parent compound. A single-crystal X-ray diffraction study confirmed the trigonal R3¯m space group and the hexagonal lattice parameters a=2.8107(5) Å, c=14.2235(6) Å, and c/a=5.060 for Li_0.68CoO₂; a=2.8090(15) Å, c=14.3890(17) Å, and c/a=5.122 for Li_0.48CoO₂; and a=2.8070(12) Å, c=14.4359(14) Å, and c/a=5.143 for Li_0.35CoO₂. The crystal structures were refined to the conventional values R=1.99% and wR=1.88% for Li_0.68CoO₂; R=2.40% and wR=2.58% for Li_0.48CoO₂; and R=2.63% and wR=2.56% for Li_0.35CoO₂. The oxygen-oxygen contact distance in the CoO₆ octahedron was determined to be shortened by the delithiation from 2.6180(9) Å in LiCoO₂ to 2.5385(15) Å in Li_0.35CoO₂. The electron density distributions of these Li_xCoO₂ crystals were analyzed by the maximum entropy method (MEM) using the present single-crystal X-ray diffraction data at 300 K. From the results of the single-crystal MEM, strong covalent bonding was clearly visible between the Co and O atoms, while no bonding was found around the Li atoms in these compounds. The gradual decrease in the electron density at the Li site upon delithiation could be precisely analyzed.     

Inhomogeneous electron liquid in the free-space building block Li2C2 plus its dimer and trimer

Quantum-chemical calculations are first reported on the building block Li₂C₂. Two low-lying isomers are predicted, and hence the equilibrium ground-state geometry by the coupled cluster method (CCSD). The ground-state is non-linear, contrasting with the other planar isomer. The dimer (Li₂C₂)₂ is then examined by the Hartree–Fock plus second-order Møller–Plesset (HF+MP2) method. The ground-state geometry is predicted to have C₄ on a linear chain. As to the trimer, the C₆ atoms are predicted at the same ab initio level to lie on a hexagon. But the Li atoms prefer each to bond to two C atoms, rather than reproduce the geometry of benzene. Finally, some contact is made with a recent density functional theory study of solid lithium carbide under pressure.     

The influence of electron correlation on reaction energies. The dimerization energies of BH3 and LiH

Results of rigorous computations employing extended Gaussian-type basis sets are reported for BH₃, B₂H₆, LiH, and Li₂H₂ in their respective equilibrium geometries. The dimerization energy of BH₃ is calculated as −20.7 kcal/mol within the Hartree-Fock approximation and as −36.6 kcal/mol if electron correlation is included. The corresponding results for the dimerization of LiH are −47.3 kcal/mol and −48.3 kcal/mol. Partitioning of the correlation energy contributions allows to attribute the effect of electron correlation to the increase of next neighbour bond interactions on the dimerization of BH₃ and LiH. The difficulties of accurate computations of reaction energies are discussed in detail.     

Crystal growth, structure determination, and optical properties of new potassium-rare-earth silicates K3RESi2O7 (RE=Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu)

Single crystals of K₃RESi₂O₇ (RE=Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were grown from a potassium fluoride flux. Two different structure types were found for this series. Silicates containing the larger rare earths, RE=Gd, Tb, Dy, Ho, Er, Tm, Yb crystallize in a structure K₃RESi₂O₇ that contains the rare-earth cation in both a slightly distorted octahedral and an ideal trigonal prismatic coordination environment, while in K₃LuSi₂O₇, containing the smallest of the rare earths, lutetium is found solely in an octahedral coordination environment. The structure of K₃LuSi₂O₇ crystallizes in space group P6₃/mmc with a=5.71160(10) Å and c=13.8883(6) Å. The structures containing the remaining rare earths crystallize in the space group P6₃/mcm with the lattice parameters of a=9.9359(2) Å, c=14.4295(4) Å, (K₃GdSi₂O₇); a=9.88730(10) Å, c=14.3856(3) Å, (K₃TbSi₂O₇); a=9.8673(2) Å, c=14.3572(4) Å, (K₃DySi₂O₇); a=9.8408(3) Å, c=14.3206(6) Å, (K₃HoSi₂O₇); a=9.82120(10) Å, c=14.2986(2) Å, (K₃ErSi₂O₇); a=9.80200(10) Å, c=14.2863(4) Å, (K₃TmSi₂O₇); a=9.78190(10) Å, c=14.2401(3) Å, (K₃YbSi₂O₇). The optical properties of the silicates were investigated and K₃TbSi₂O₇ was found to fluoresce in the visible.     

Preparation of hollow nanospheres g-C3N4 loaded by Keggin type Cu mono-substituted heteropoly acid with enhanced visible-light harvesting and electron transfer properties for high-efficiency photocatalysis

Abstract

A series of heterojunction catalysts (CuCN-X) were successfully fabricated by loading the different amounts of Keggin type Cu mono-substituted heteropoly acid (HPW₁₁Cu) on the surface of hollow nanospheres g-C₃N₄ (HSCN). The HSCNs were prepared by using SiO₂ as a hard template. The chemical structure, porosity, morphology and electronic property of the prepared catalysts were investigated using XRD, SEM, N₂-absorption isotherm and XPS. The results indicated that the modified HSCN show prominent absorption in the visible light range and decrease the band gap. The greatly enhanced photocatalytic activity of obtained CuCN-X have been shown by the degradation of Rhodamine B (RhB), reduction of CO₂ and production of photocatalytic hydrogen under visible light irradiation. More significantly, CuCN-15 has shown significantly improved photocatalytic performance at 4.5, 3.5 and 3.3 times higher that of than HSCN for the degradation of RhB, reduction of CO₂ and production of photocatalytic hydrogen, respectively. Furthermore, the mechanism for the enhanced photocatalytic activity of CuCN-X is proposed to be due to the formation of heterojunction. The electrons can be rapidly transferred from HSCN to HPW₁₁Cu, in which facilitate charge separation and charge transfer.     

Pulse radiolysis study of trapped electron in MgSO4.7H2O single crystal

The single crystal of MgSO₄.7H₂O is very interesting to study the structure and kinetics of trapped electron in solids, because the hydrated salt has many H₂O molecules in the crystal lattice like water. The pulse radiolysis study of the trapped electrons in MgSO₄.7H₂O single crystal was carried out based on an electron linear accelerator. Two optical absorption peaks of the trapped electron in MgSO₄.7H₂O single crystal were observed: one is at the wavelength of 600 nm with a short lifetime of 81.4 ns; another is at 400 nm with a long lifetime of 1.06 μs. The kinetics of the trapped electron in the crystal was also compared with that in the aqueous solution.     

Photoinduced electron transfer in some photosensitive molecules-incorporated semiconductor/zeolites: New photocatalytic systems

An intramolecular charge transfer (ICT) molecule,p-N,N-dimethyl-aminobenzoic acid (DMABA) has been studied in zeolite and colloidal media. The ratio of ICT to normal emission (ICT/LE) is greatly enhanced in zeolites compared to that in polar solvents. The ICT emission of DMABA was quenched by increasing the concentration of TiO₂ colloids, while the normal emission was slightly enhanced. Upon illumination of the heteropoly acid (HPA) incorporated TiO₂ colloids, interfacial electron transfer takes place from the conduction band of TiO₂ to the incorporated HPA which is also excited to catalyze the photoreduction of Methyl Orange. It is found that the interfacial electron transfer mechanism of HPA/TiO₂ is quite analogous to the Z-scheme mechanism for plant photosynthetic systems. In DMABA-adsorbed TiO₂/Y-zeolite the ICT/LE ratio of DMABA is quite small implying that electron transfer takes place from DMABA to the conduction band of TiO₂. This results in drastic enhancement in the photocatalytic activity of DMABA-adsorbed TiO₂/Y-zeolite compared to free TiO₂/Y-zeolite.     

Crystal structure of Sr3Ir2O7 investigated by transmission electron microscopy

We report on the crystallographic structure of the layered perovskite iridate Sr₃Ir₂O₇, investigated using transmission electron microscopy. The space group was found to be Bbcb (, No. 68 in the International Tables for Crystallography) at 315 K. A very fine twin structure with 90° rotation with respect to the c-axis was observed. The crystal structure at temperatures lower than 285 K, where a phase transition from paramagnetism to weak ferromagnetism is known to occur, was also examined. There was no difference in the extinction rule for the diffraction patterns between the two phases. We conclude that there is no change in the space group for this magnetic transition. There still remains the possibility of a change in the rotation angle of IrO₆ octahedrons and a corresponding change in the interatomic distance between Ir and O, though.     

A combined temperature-dependent electron and single-crystal X-ray diffraction study of the fresnoite compound Rb2VV2O8

High-purity Rb₂V₃O₈ has been grown and temperature-dependent electron and single-crystal X-ray diffraction used to carefully investigate its fresnoite-type reciprocal lattice. In contrast to other recently investigated representatives of the fresnoite family of compounds, Rb₂V₃O₈ is not incommensurately modulated with an incommensurate basal plane primary modulation wave vector given by q∼0.3 〈110〉^*. A careful low-temperature electron diffraction study has, however, revealed the existence of weak incommensurate satellite reflections characterized by the primitive primary modulation wave vector q₁∼0.16c^*. The reciprocal space positioning of these incommensurate satellite reflections, the overall (3+1)-d superspace group symmetry, as well as the shapes of the refined displacement ellipsoids determined from single-crystal XRD refinement, are all consistent with their arising from a distinct type of condensed rigid unit modes (RUMs) of distortion of the Rb₂V₃O₈ parent structure.     

High-resolution transmission electron microscopy investigation of nanostructures in SnO2 thin films prepared by pulsed laser deposition

Pulsed laser deposition (PLD) was used to grow nanocrystalline SnO₂ thin films onto glass substrates. The nanocrystallites and microstructures in SnO₂ thin films grown by PLD techniques have been investigated in detail by using X-ray diffraction and high-resolution transmission electron microscopy (HRTEM). The PLD process was carried out at room temperature under a working pressure of about 2×10⁻⁶ mbar. Experimental results indicate that thin films are composed of a polycrystalline SnO₂ and an amorphous SnO phase. In particular, the presence of such an amorphous SnO phase in the thin films greatly limits their practical use as gas-sensing devices. HRTEM observations revealed that SnO₂ nanocrystallites with tetragonal rutile structure embed in an amorphous SnO matrix, which are approximatively equiaxed. These approximatively equiaxed SnO₂ nanocrystallites contain a high density of defects, such as twin boundaries and edge dislocations. The grain growth of SnO₂ thin films may be discussed in terms of the coalescent particle growth mechanism.     

Structural analysis of SiO2 gel films by high energy electron diffraction

The structure of SiO₂ gel-films prepared from acid and basic TEOS solutions is analyzed by high energy transmission electron diffraction method. The Si-O bond length of gel-films is 1.58 to 1.60 Å, which is shorter than that of vitreous silica (1.61 Å) but similar to that of 80 Å thick evaporated a-SiO₂ film. An atomic pair peak with 0.81 Å distance exists on the reduced radial distribution functions of the gel-films, which is believed to be O-H, but being smaller than that of H₂O (0.969 Å).     

The Synthesis, Characterization and Microwave Properties of ZnCo-Substituted W-Type Barium Hexaferrite, from a Sol-Gel Precursor

The preparation of BaZn_{2 – x} Co _x Fe₁₆O₂₇ W-type hexaferrites powders by a citrate sol-gel method has been investigated. The samples were characterized by TG-DSC, X-ray diffraction (XRD), scanning electron microscopy (SEM). The complex dielectric constant and complex permeability of hexaferrite-paraffin wax composites were measured by the transmission/reflection coaxial line method in the range from 50 MHz to 3 GHz. The dependence of complex dielectric constant and permeability on annealing temperature, composition and measuring frequency was presented.     

First single electron transfer reaction on propargylic chloride in 5-nitroimidazole series

We report here the first example of an S_RN1 reaction on propargylic chloride in heterocyclic series. The reaction of 4-(3-chloroprop-1-ynyl)-1,2-dimethyl-5-nitro-1H-imidazole with nitronate anions led to both the formation of the C-alkylated product through an S_RN1 mechanism and the predominant ethylenic compound resulting from nitrous acid elimination on the C-alkylated product. Interestingly, in contrast to our previous works on S_RN1 reactivity, no O-alkylated product was observed.