Photocatalysis on Fine Powders of Perovskite Oxides

Fine powders of semiconductor oxides have been widely used as photocatalysts for many reactions. Among the various photocatalytic reactions, water splitting has been given much importance, since it is a promising chemical route for solar energy conversion. Perovskite oxides, in particular SrTiO, have been commonly used as photocatalysts because some of them can decompose H,O into H, and 0, without an external bias potential (1). In turn, this is because the conduction band (CB) edges of some of the perovskite oxides are more negative than the H+/H, energy level. Since the catalytic activity is related to the surface properties of the solids, fine powders rather than single crystals are used. Photocatalysis on fine powers can be conveniently discussed in three parts, viz. preparation, characterization and their catalytic activity. Presently, photo-decomposition of water using SrTiO, fine powders is discussed in greater detail, although other photocatalytic reactions on various perovskite oxides are also briefly dealt with.

PES studies of semiconductor - metal transitions in metal oxides

Semiconductor-Metal transitions in Ti2O3, VO2, V2O3 and Ti3O5 have been investigated employing X-ray and UV Photoelectron spectroscopy. The transitions are accompanied by significant changes in the 3d band of the transition metals as well as some of the core levels.

Unusual effects of anisotropic bonding in Cu(II) and Ni(II) oxides with K2NiF4 structure

Geometric constraints present in A2BO4 compounds with the tetragonal-T structure of K2NiF4 impose a strong pressure on the B---OII---B bonds and a stretching of the A---OI---A bonds in the basal planes if the tolerance factor is t congruent with RAO/√2 RBO < 1, where RAO and RBO are the sums of the A---O and B---O ionic radii. The tetragonal-T phase of La2NiO4 becomes monoclinic for Pr2NiO4, orthorhombic for La2CuO4, and tetragonal-T′ for Pr2CuO4. The atomic displacements in these distorted phases are discussed and rationalized in terms of the chemistry of the various compounds. The strong pressure on the B---OII---B bonds produces itinerant σ*x2−y2 bands and a relative stabilization of localized dz2 orbitals. Magnetic susceptibility and transport data reveal an intersection of the Fermi energy with the d2z2 levels for half the copper ions in La2CuO4; this intersection is responsible for an intrinsic localized moment associated with a configuration fluctuation; below 200 K the localized moment smoothly vanishes with decreasing temperature as the d2z2 level becomes filled. In La2NiO4, the localized moments for half-filled dz2 orbitals induce strong correlations among the σ*x2−y2 electrons above Td reverse similar, equals 200 K; at lower temperatures the σ*x2−y2 electrons appear to contribute nothing to the magnetic susceptibility, which obeys a Curie-Weiss law giving a μeff corresponding to S = 1/2, but shows no magnetic order to lowest temperatures. These surprising results are verified by comparison with the mixed systems La2Ni1−xCuxO4 and La2−2xSr2xNi1−xTixO4. The onset of a charge-density wave below 200 K is proposed for both La2CuO4 and La2NiO4, but the atomic displacements would be short-range cooperative in mixed systems. The semiconductor-metallic transitions observed in several systems are found in many cases to obey the relation Ea reverse similar, equals kTmin, where varrho = varrho0exp(−Ea/kT) and Tmin is the temperature of minimum resistivity varrho. This relation is interpreted in terms of a diffusive charge-carrier mobility with Ea reverse similar, equals ΔHm reverse similar, equals kT at T = Tmin.

Doping Transition Metal (Mn or Cu) Ions in Semiconductor Nanocrystals

Following growth doping strategy and using dopant oxides nanocrystals as dopant sources, we report here two different transition-metal ions doped in a variety of group II-VI semiconductor nanocrystals. Using manganese oxide and copper oxide nanocrystals as corresponding dopant sources, intense photoluminescence emission over a wide range of wavelength has been observed for different host nanocrystals. Interestingly, this single doping strategy is successful in providing such highly emissive nanocrystals considered here, in contrast with the literature reports that would suggest synthesis strategies to be highly specific to the particular dopant, host, or both. We investigate and discuss the possible mechanism of the doping process, supporting the migration of dopant ions from dopant oxide nanocrystals to host nanocrystals as the most likely scenario.

Virtues of marginally metallic oxides

Transition-metal oxides at the metal-insulator boundary, especially those belonging to the perovskite family, exhibit fascinating phenomena such as insulator-metal transitions controlled by composition, high-temperature superconductivity and giant magnetoresistance (GMR), Interestingly, many of these marginally metallic oxides obey the established criteria for metallicity and have a finite density of states at the Fermi;level. The perovskite manganates exhibiting GMR, on the other hand, are unusual in that they possess very high resistivities in the 'metallic' state and show no significant density of states at the Fermi level, Marginal metallicity in oxide systems is a problem of great complexity and contemporary interest and its understanding is of crucial significance to the diverse phenomena exhibited by these materials.

Structural and optical investigation of semiconductor CdSe/CdS core-shell quantum dot thin films

Highly luminescent CdSe/CdS core-shell nanocrystals have been assembled on indium tin oxide (ITO) coated glass substrates using a wet synthesis route. The physical properties of the quantum dots (QD) have been investigated using X-ray diffraction, transmission electron microscopy and optical absorption spectroscopy techniques. These quantum dots showed a strong enhancement in the near band edge absorption. The in situ luminescence behavior has been interpreted in the light of the quantum confinement effect and induced strain in the core-shell structure.

The dynamics of polymerized carbon nanotubes in semiconductor polymer electronics and electro-mechanical sensing

Polymerized carbon nanotubes (CNTs) are promising materials for polymer-based electronics and electro-mechanical sensors. The advantage of having a polymer nanolayer on CNTs widens the scope for functionalizing it in various ways for polymer electronic devices. However, in this paper, we show for the first time experimentally that, due to a resistive polymer layer having carbon nanoparticle inclusions and polymerized carbon nanotubes, an interesting dynamics can be exploited. We first show analytically that the relative change in the resistance of a single isolated semiconductive nanotube is directly proportional to the axial and torsional dynamic strains, when the strains are small, whereas, in polymerized CNTs, the viscoelasticity of the polymer and its effective electrical polarization give rise to nonlinear effects as a function of frequency and bias voltage. A simplified formula is derived to account for these effects and validated in the light of experimental results. CNT–polymer-based channels have been fabricated on a PZT substrate. Strain sensing performance of such a one-dimensional channel structure is reported. For a single frequency modulated sine pulse as input, which is common in elastic and acoustic wave-based diagnostics, imaging, microwave devices, energy harvesting, etc, the performance of the fabricated channel has been found to be promising.

Electrical and mechanical properties of diluted magnetic semiconductor Zn1-xMnxS nanocrystalline films

Nanostructured Zn1-xMnxS films (0 less-than-or-equals, slant x less-than-or-equals, slant 0.25) were deposited on glass substrates by simple resistive thermal evaporation technique. All the films were deposited at 300 K in a vacuum of 2*10-6 m bar. All the films temperature dependence of resistivity revealed semiconducting behaviour of the samples. Hot probe test revealed that all the samples exhibited n-type conductivity. The nanohardness of the films ranges from 4.7 to 9.9 GPa, Young's modulus value ranging 69.7-94.2 GPa.

Relative Stabilities of Layered Perovskite and Pyrochlore Structures in Transition Metal-Oxides Containing Trivalent Bismuth

In order to investigate the factors determining the relative stabilities of layered perovskite and pyrochlore structures of transition metal oxides containing trivalent bismuth, several ternary and quaternary oxides have been investigated. While d0 cations stabilize the layered perovskite structure, cations containing partially-filled d orbitals (which suppress ferroelectric distortion of MO6 octahedra) seem to favor pyrochlore-related structures. Thus, the vanadium analogue of the layered perovskite Bi4Ti3O12 cannot be prepared; instead the composition consists of a mixture of pyrochlore-type Bi1.33V2O6, Bi2O3, and Bi metal. The distortion of Bi1.33V2O6 to orthorhombic symmetry is probably due to an ordering of anion vacancies in the pyrochlore structure. None of the other pyrochlores investigated, Bi2NbCrO7, Bi2NbFeO7, TlBiM2O7 (M = Nb, Ta), shows evidence for cation ordering in the X-Ray diffraction patterns, as indeed established by structure refinement of TlBiNb2O7.

Action of Transition Metal Oxides on Composite Solid Propellants

The catalytic effects of Fe2O3, Ni2O3, MnO2, and Co2O3 transition metal oxides (TMO) on the combustion of polystyrene and carboxyl-terminated polybutadiene were investigated. The order of activity of TMO's was explained by the presence of Co and absence of Fe and Ni in their lattice systems along with a reduced electron-transfer process; in systems which induce the metal ions to enter the lattice, the electron transfer process is much greater. The thermal decomposition of ammonium perchlorate propellants was enhanced to a greater extent by Co2O3 and MnO2 than by Fe2O3 and Ni2O3.

High-temperature superconductivity in La- and Lu-substituted YBa2,Cu3,O7, and related oxides

The perovskites, Y0.75La0.25Ba2Cu3O7 and Y0.75Lu0.25Ba2Cu3O7, show high-Tc superconductivity (with zero resistance at or above 80 K), just as the parent compound YBa2Cu3O7. The Lu-substituted oxide, with the smallest unit-cell parameters, shows the highest Tc besides exhibiting a 100% Meissner effect. Hc1, in these oxides is around 25 mT, but the Hc2, is large. The thermopower of YBa2Cu3O7 shows a sharp transition to zero at the superconducting transition, reinforcing the bulk nature of the superconductivity. Preliminary studies show that ErBa2Cu3O7 and Er0.5Y0.5Ba2Cu3O7 are both high-temperature superconductors with zero resistance in the 82-90 K range.

HIGH-Tc superconductivity in perovskite oxides of the Y-Ba-Cu-O system

Several biphasic compositions of the type Y3-xBa3+xCu6O14 show an onset of superconductivity in the 90-115K range, attaining zero resistance in the 70-85K range. The phase responsible for superconductivity in these compositions is a perovskite oxide of composition YBa2Cu3 O7. This oxide annealed in oxygen shows the onset of superconductivity at 120K and zero resistance at 87K. YBa2,Cu3O7 shows the highest Meissner effect of all oxide superconductors. The superconducting behaviour of the two perovskite oxides, Y0.95Ba1.95,Cu3O7 and Y1.05Ba1.95Cu3O7 show interesting features; a marked decrease in resistivity is observed from room temperature itself in the former oxide with zero resistance at 89K. Electron microscopy and infrared spectra of these oxides are briefly discussed.

Mechanism of catalytic activity of metal oxides and chromites on ammonium perchlorate pyrolysis

This study investigates the mechanism of action of transition metal chromites on the decomposition of ammonium perchlorate.

HNbWO6 and HTaWO6: Novel oxides related to ReO3 formed by ion exchange of rutile-type LiNbWO6 and LiTaWO6

Both LiNbWO6 and LiTaWO6 undergo ion exchange in hot aqueous H2SO4 yielding the hydrates HMWO6 · H2O (M = Nb or Ta). The reaction is accompanied by a structural transformation from the rutile to the ReO3 structure. The cell constants are a = 3.783(3)Å for HNbWO6 · H2O and a = 3.785(5)Å for HTaWO6 · H2O. The ReO3 structure is retained by the dehydration products HMWO6 and MWO5.5 as well. HMWO6 phases yield H1+xMWO6 hydrogen bronzes on exposure to hydrogen in the presence of platinum catalyst.