Vanadia Supported on Rice Husk Silica Promoted Rare Earth Oxides

The selective oxidation of alkylaromatics is one of the main processes since the reaction products are important as intermediates in numerous industrial organic chemicals. Side-chain oxidation of alkyl aromatic compounds catalyzed by heterogeneous catalysts using cleaner peroxide oxidants is an especially attractive goal since classical synthetic laboratory procedures preferably use permanganate or acid dichromate as stoichiometric oxidants. In spite of many studies, there are very few which use hydrogen peroxide as a source of oxygen in the C-H activation of alkanes. Eflective utilization of ethylbenzene, available in the xylene stream of the petrochemical industry to more value added products is a promising one in chemical industry. The oxidation products of ethylbenzene are widely employed as intermediates in organic, steroid and resin synthesis.

Magnetic field effect on quantum corrections to the low-temperature conductivity in mettalic perovskite oxides

The transport and magnetotransport properties of the metallic and ferromagnetic SrRuO3 (SRO) and the metallic and paramagnetic LaNiO3 (LNO) epitaxial thin films have been investigated in fields up to 55 T at temperatures down to 1.8 K . At low temperatures both samples display a well-defined resistivity minimum. We argue that this behavior is due to the increasing relevance of quantum corrections to the conductivity (QCC) as temperature is lowered; this effect being particularly relevant in these oxides due to their short mean free path. However, it is not straightforward to discriminate between contributions of weak localization and renormalization of electron-electron interactions to the QCC through temperature dependence alone. We have taken advantage of the distinct effect of a magnetic field on both mechanisms to demonstrate that in ferromagnetic SRO the weak-localization contribution is suppressed by the large internal field leaving only renormalized electron-electron interactions, whereas in the nonmagnetic LNO thin films the weak-localization term is relevant.

Surface electron properties and catalytic activity of rare earth oxides

The rare earths have provided fascinating field for chemists confronted with problems of their separation and purification. The rare earths become available in relatively pure form in recent years due to the development of efficient separation methods, largely as a byproduct of the atomic energy programmes of various countries. The rare earths often called lanthanides from La (Z=57) to Lu (Z=7l) display subtle variation of properties through the series, while the differences become appreciable for the elements that are farther apart.

Studies on the catalysis by sulfated mixed oxides of tin with some rare earth elements

A comparative study of acid-base properties and catalytic activity of Sn-La and Sn-Sm mixed oxides and their corresponding sulfate modified analogues are reported in this thesis. The catalytic activity and product selectivity in the decomposition of alcohols are correlated with the acid-base and redox properties of the catalyst systems under study The effect of catalyst preparation, pretreatment and various reaction parameters on the catalytic activity of sulfate modified oxides is investigated in the oxidative dehydrogenation reactions The experimental conditions are optimised to synthesise industrially important organic chemicals viz. 2,6 xylenol, o-cresol, N-methylanilne and N,N-dimethylaniline employing the mixed oxide systems. The effect of sulfate treatment on the catalytic activity of these systems in the alkylation reactions of phenol, anisole and aniline is also investigated and the merits and demerits of sulfate treatment are highlighted.

Rigorous characterization of oxygen vacancies in ionic oxides

Charged and neutral oxygen vacancies in the bulk and on perfect and defective surfaces of MgO are characterized as quantum-mechanical subsystems chemically bonded to the host lattice and containing most of the charge left by the removed oxygens. Attractors of the electron density appear inside the vacancy, a necessary condition for the existence of a subsystem according to the atoms in molecules theory. The analysis of the electron localization function also shows attractors at the vacancy sites, which are associated to a localization basin shared with the valence domain of the nearest oxygens. This polyatomic superanion exhibits chemical trends guided by the formal charge and the coordination of the vacancy. The topological approach is shown to be essential to understand and predict the nature and chemical reactivity of these objects. There is not a vacancy but a coreless pseudoanion that behaves as an activated host oxygen.

First principles LDA+U and GGA+U study of cerium oxides: Dependence on the effective U-parameter

The electronic structure and properties of cerium oxides (CeO2 and Ce2O3) have been studied in the framework of the LDA+U and GGA(PW91)+U implementations of density functional theory. The dependence of selected observables of these materials on the effective U parameter has been investigated in detail. The examined properties include lattice constants, bulk moduli, density of states, and formation energies of CeO2 and Ce2O3. For CeO2, the LDA+U results are in better agreement with experiment than the GGA+U results whereas for the computationally more demanding Ce2O3 both approaches give comparable accuracy. Furthermore, as expected, Ce2O3 is much more sensitive to the choice of the U value. Generally, the PW91 functional provides an optimal agreement with experiment at lower U energies than LDA does. In order to achieve a balanced description of both kinds of materials, and also of nonstoichiometric CeO2¿x phases, an appropriate choice of U is suggested for LDA+U and GGA+U schemes. Nevertheless, an optimum value appears to be property dependent, especially for Ce2O3. Optimum U values are found to be, in general, larger than values determined previously in a self-consistent way.

Ionic-covalent transition in titanium oxides

The nature of the chemical bond in three titanium oxides of different crystal structure and different formal oxidation state has been studied by means of the ab initio cluster-model approach. The covalent and ionic contributions to the bond have been measured from different theoretical techniques. All the analysis is consistent with an increasing of covalence in the TiO, Ti2O3, and TiO2 series as expected from chemical intuition. Moreover, the use of the ab initio cluster-model approach combined with different theoretical techniques has permitted us to quantify the degree of ionic character, showing that while TiO can approximately be described as an ionic compound, TiO2 is better viewed as a rather covalent oxide.

Investigations on novel polymer nano composites and bio-compatible manganese doped ZnS nanocrystals for photonic and bio-imaging applications

Fluorescence is a powerful tool in biological research, the relevance of which relies greatly on the availability of sensitive and selective fluorescent probes. Nanometer sized fluorescent semiconductor materials have attracted considerable attention in recent years due to the high luminescence intensity, low photobleaching, large Stokes’ shift and high photochemical stability. The optical and spectroscopic features of nanoparticles make them very convincing alternatives to traditional fluorophores in a range of applications. Efficient surface capping agents make these nanocrystals bio-compatible. They can provide a novel platform on which many biomolecules such as DNA, RNA and proteins can be covalently linked. In the second phase of the present work, bio-compatible, fluorescent, manganese doped ZnS (ZnS:Mn) nanocrystals suitable for bioimaging applications have been developed and their cytocompatibility has been assessed. Functionalization of ZnS:Mn nanocrystals by safe materials results in considerable reduction of toxicity and allows conjugation with specific biomolecules. The highly fluorescent, bio-compatible and water- dispersible ZnS:Mn nanocrystals are found to be ideal fluorescent probes for biological labeling

An investigation on the preparation and properties of some transparent conducting oxides and lead selenide thin films”

The investigation of physical properties of matter has progressed so much during the last hundred years. Today physics is divided in to a large distinct group of special branches. These branches are distinguished by the particular area studied, method of investigation and so on. An independent and important branch that has developed is the physics ofthin films.Any object in solid or liquid form with one of its dimensions very much smaller than that of the other two may be called a thin film. It is having only one common property, namely, one of their dimensions is very small, though all their physical properties may be different. Thin layers of oil, floating on the surface of water, with their fascinating colours, have attracted men’s curiosity from time immemorial. The earliest application of thin films was the protective coatings in the form of paints. A thin layer of tin has been used from ancient times to protect copper utensils from corrosion. Indium thin films are used in certain applications on account of their good lubricating property. Relay contacts are coated with thin films of rare earth metals in order to prevent burning due to arcing. Hard coatings are also available using diamond like carbon (i-carbon). The basic properties of thin films are of considerable interest because of their potential applications in various fields of science and technology

Acid-Base. Surface Electron Donatin6 &.Catai.Ytlc Properties Of Some Binary Mixed Oxides Containing Rare Earth Elements

Catalysis research underpins the science of modern chemical processing and fuel technologies. Catalysis is commercially one of the most important technologies in national economies. Solid state heterogeneous catalyst materials such as metal oxides and metal particles on ceramic oxide substrates are most common. They are typically used with commodity gases and liquid reactants. Selective oxidation catalysts of hydrocarbon feedstocks is the dominant process of converting them to key industrial chemicals, polymers and energy sources.[1] In the absence of a unique successfiil theory of heterogeneous catalysis, attempts are being made to correlate catalytic activity with some specific properties of the solid surface. Such correlations help to narrow down the search for a good catalyst for a given reaction. The heterogeneous catalytic performance of material depends on many factors such as [2] Crystal and surface structure of the catalyst. Thermodynamic stability of the catalyst and the reactant. Acid- base properties of the solid surface. Surface defect properties of the catalyst.Electronic and semiconducting properties and the band structure. Co-existence of dilferent types of ions or structures. Adsorption sites and adsorbed species such as oxygen.Preparation method of catalyst , surface area and nature of heat treatment. Molecular structure of the reactants. Many systematic investigations have been performed to correlate catalytic performances with the above mentioned properties. Many of these investigations remain isolated and further research is needed to bridge the gap in the present knowledge of the field.

Development of p-type transparent semiconducting oxides for thin film transistor applications

Semiconductor physics has developed significantly in the field of re- search and industry in the past few decades due to it’s numerous practical applications. One of the relevant fields of current interest in material science is the fundamental aspects and applications of semi- conducting transparent thin films. Transparent conductors show the properties of transparency and conductivity simultaneously. As far as the band structure is concerned, the combination of the these two properties in the same material is contradictory. Generally a trans- parent material is an insulator having completely filled valence and empty conduction bands. Metallic conductivity come out when the Fermi level lies within a band with a large density of states to provide high carrier concentration. Effective transparent conductors must nec- essarily represent a compromise between a better transmission within the visible spectral range and a controlled but useful electrical con- ductivity [1–6]. Generally oxides like In2O3, SnO2, ZnO, CdO etc, show such a combination. These materials without any doping are insulators with optical band gap of about 3 eV. To become a trans- parent conductor, these materials must be degenerately doped to lift the Fermi level up into the conduction band. Degenerate doping pro- vides high mobility of extra carriers and low optical absorption. The increase in conductivity involves an increase in either carrier concen- tration or mobility. Increase in carrier concentration will enhance the absorption in the visible region while increase in mobility has no re- verse effect on optical properties. Therefore the focus of research for new transparent conducting oxide (TCO) materials is on developing materials with higher carrier mobilities.

Evidence for polaron conduction in nanostructured manganese ferrite

Nanoparticles of manganese ferrite were prepared by the chemical co-precipitation technique. The dielectric parameters, namely, real and imaginary dielectric permittivity (ε and ε ), ac conductivity (σac) and dielectric loss tangent (tan δ), were measured in the frequency range of 100 kHz–8MHz at different temperatures. The variations of dielectric dispersion (ε ) and dielectric absorption (ε ) with frequency and temperature were also investigated. The variation of dielectric permittivity with frequency and temperature followed the Maxwell–Wagner model based on interfacial polarization in consonance with Koops phenomenological theory. The dielectric loss tangent and hence ε exhibited a relaxation at certain frequencies and at relatively higher temperatures. The dispersion of dielectric permittivity and broadening of the dielectric absorption suggest the possibility of a distribution of relaxation time and the existence of multiple equilibrium states in manganese ferrite. The activation energy estimated from the dielectric relaxation is found to be high and is characteristic of polaron conduction in the nanosized manganese ferrite. The ac conductivity followed a power law dependence σac = Bωn typical of charge transport assisted by a hopping or tunnelling process. The observed minimum in the temperature dependence of the frequency exponent n strongly suggests that tunnelling of the large polarons is the dominant transport process

On the dielectric dispersion and absorption in nanosized manganese zinc mixed ferrites

The temperature and frequency dependence of dielectric permittivity and dielectric loss of nanosized Mn1−xZnxFe2O4 (for x = 0, 0.2, 0.4, 0.6, 0.8, 1) were investigated. The impact of zinc substitution on the dielectric properties of the mixed ferrite is elucidated. Strong dielectric dispersion and broad relaxation were exhibited by Mn1−xZnxFe2O4. The variation of dielectric relaxation time with temperature suggests the involvement of multiple relaxation processes. Cole–Cole plots were employed as an effective tool for studying the observed phenomenon. The activation energies were calculated from relaxation peaks and Cole–Cole plots and found to be consistent with each other and indicative of a polaron conduction

Mechanism of ac conduction in nanostructured manganese zinc mixed ferrites

Mn1−xZnxFe2O4 nanoparticles (x = 0 to 1) were synthesized by the wet chemical co-precipitation technique. X-ray diffraction and transmission electron microscopy and high resolution transmission electron microscopy were effectively utilized to investigate the different structural parameters. The ac conductivity of nanosized Mn1−xZnxFe2O4 were investigated as a function of frequency, temperature and composition. The frequency dependence of ac conductivity is analysed by the power law σ(ω)ac = Bωn which is typical for charge transport by hopping or tunnelling processes. The temperature dependence of frequency exponent n was investigated to understand the conduction mechanism in different compositions. The conduction mechanisms are mainly based on polaron hopping conduction

Contact potential induced enhancement of magnetization in polyaniline coated nanomagnetic iron oxides by plasma polymerization

The present work derives motivation from the so called surface/interfacial magnetism in core shell structures and commercial samples of Fe3O4 and c Fe2O3 with sizes ranging from 20 to 30 nm were coated with polyaniline using plasma polymerization and studied. The High Resolution Transmission Electron Microscopy images indicate a core shell structure after polyaniline coating and exhibited an increase in saturation magnetization by 2 emu/g. For confirmation, plasma polymerization was performed on maghemite nanoparticles which also exhibited an increase in saturation magnetization. This enhanced magnetization is rather surprising and the reason is found to be an interfacial phenomenon resulting from a contact potential.