Stable Dispersions of Metal Oxide Nanowires and Nanoparticles in Water, Dimethylformamide and Toluene

In view of the important need to generate well-dispersed inorganic nanostructures in various solvents, we have explored the dispersion of nanostructures of metal oxides such as TiO2, Fe3O4 and ZnO in solvents of differing polarity in the presence of several surfactants. The solvents used are water, dimethylformamide (DMF) and toluene. The surfactant-solvent combinations yielding the best dispersions are reported alongwith some of the characteristics of the nanostructures in the dispersions. The surfactants which dispersed TiO2 nanowires in water were polyethylene oxide (PEO), Triton X-100 (TX-100), polyvinyl alcohol (PVA) and sodium bis(2-ethylhexyl) sulphosuccinate (AOT). TiO2 nanoparticles could also be dispersed with AOT and PEO in water, and with AOT in toluene. In DMF, PVA, PEO and TX-100 were found to be effective, while in toluene, only AOT gave good dispersions. Fe3O4 nanoparticles were held for long periods of time in water by PEO, AOT, PVA and polyethylene glycol (PEG), and by AOT in toluene. In the case of ZnO nanowires, the best surfactant-solvent combinations were found to be, PEO, sodium dodecyl sulphate (SIDS) and AOT in water and AOT, PEG, PVA, PEO and TX-100 in DMF In toluene, stable dispersions of ZnO nanowires were obtained with PEO. We have also been able to disperse oxide nanostructures in non-polar solvents by employing a hydrophobic silane coating on the surface.

Schiff Base Complexes and their Assemblies on Surfaces

Schiff bases and their transition metal complexes are of significant current interest even though they have been prepared for decades. They have been used in various applications such as catalysis, corrosion protection, and molecular sensors. In this study, N-aryl Schiff base ketimine ligands as well as numerous new, differently substituted salen and salophen-type ligands and their cobalt(II), copper(II), iron(II), manganese(II), and nickel(II) complexes were synthesised. New solid state structures of the above compounds and the dioxygen coordination properties of cobalt(II) complexes and catalytic properties of three synthesised binuclear complexes were examined. The prepared complexes were applied in the formation of self-assembled layers on a polycrystalline gold surface and liquid-graphite interface. The effect of metal ion and ligand structure on the as-formed patterns was studied. When studying gold surfaces, a unique thiol-assisted dissolution of elemental gold was observed and a new thin gold foil preparation method was introduced. In the summary, synthesis, structures, and properties of Schiff base ligands and their transition metal complexes are described in detail and the applications of these reviewed. Assemblies of other complexes on a liquid-graphite interface and on a gold surface are also presented, and the surface characterisation methods and surfaces employed are described.

Mechanoformation of ammonium perchlorate-potassium perchlorate solid solutions

Ammonium perchlorate-potassium perchlorate mixtures, upon pelletization, form a series of homogeneous solid solutions as manifested by X-ray powder diffractograms. Scanning electron microscopic studies throw light on the mechanism of the solid-solution formation. Solid solutions of ammonium perchlorate-potassium perchlorate have also been obtained by a modified cocrystallization technique. The thermal and combustion behavior of the solid solutions have also been studied, using the DTA technique and the Crawford strand burner.

On the valence state of molybdenum in Ce2MoO6

he valence state of molybdenum in cubic Ce2MoO6 was investigated using magnetic susceptibility measurements, electron spin resonance spectroscopy and X-ray absorption spectroscopy. The results are consistent with the formulation Ce3+Ce4+Mo5+O6.

Intermolecular Interactions of Noble-Gas-Containing Species

The importance of intermolecular interactions to chemistry, physics, and biology is difficult to overestimate. Without intermolecular forces, condensed phase matter could not form. The simplest way to categorize different types of intermolecular interactions is to describe them using van der Waals and hydrogen bonded (H-bonded) interactions. In the H-bond, the intermolecular interaction appears between a positively charged hydrogen atom and electronegative fragments and it originates from strong electrostatic interactions. H-bonding is important when considering the properties of condensed phase water and in many biological systems including the structure of DNA and proteins. Vibrational spectroscopy is a useful tool for studying complexes and the solvation of molecules. Vibrational frequency shift has been used to characterize complex formation. In an H-bonded system A∙∙∙H-X (A and X are acceptor and donor species, respectively), the vibrational frequency of the H-X stretching vibration usually decreases from its value in free H-X (red-shift). This frequency shift has been used as evidence for H-bond formation and the magnitude of the shift has been used as an indicator of the H-bonding strength. In contrast to this normal behavior are the blue-shifting H-bonds, in which the H-X vibrational frequency increases upon complex formation. In the last decade, there has been active discussion regarding these blue-shifting H-bonds. Noble-gases have been considered inert due to their limited reactivity with other elements. In the early 1930 s, Pauling predicted the stable noble-gas compounds XeF6 and KrF6. It was not until three decades later Neil Bartlett synthesized the first noble-gas compound, XePtF6, in 1962. A renaissance of noble-gas chemistry began in 1995 with the discovery of noble-gas hydride molecules at the University of Helsinki. The first hydrides were HXeCl, HXeBr, HXeI, HKrCl, and HXeH. These molecules have the general formula of HNgY, where H is a hydrogen atom, Ng is a noble-gas atom (Ar, Kr, or Xe), and Y is an electronegative fragment. At present, this class of molecules comprises 23 members including both inorganic and organic compounds. The first and only argon-containing neutral chemical compound HArF was synthesized in 2000 and its properties have since been investigated in a number of studies. A helium-containing chemical compound, HHeF, was predicted computationally, but its lifetime has been predicted to be severely limited by hydrogen tunneling. Helium and neon are the only elements in the periodic table that do not form neutral, ground state molecules. A noble-gas matrix is a useful medium in which to study unstable and reactive species including ions. A solvated proton forms a centrosymmetric NgHNg+ (Ng = Ar, Kr, and Xe) structure in a noble-gas matrix and this is probably the simplest example of a solvated proton. Interestingly, the hypothetical NeHNe+ cation is isoelectronic with the water-solvated proton H5O2+ (Zundel-ion). In addition to the NgHNg+ cations, the isoelectronic YHY- (Y = halogen atom or pseudohalogen fragment) anions have been studied with the matrix-isolation technique. These species have been known to exist in alkali metal salts (YHY)-M+ (M = alkali metal e.g. K or Na) for more than 80 years. Hydrated HF forms the FHF- structure in aqueous solutions, and these ions participate in several important chemical processes. In this thesis, studies of the intermolecular interactions of HNgY molecules and centrosymmetric ions with various species are presented. The HNgY complexes show unusual spectral features, e.g. large blue-shifts of the H-Ng stretching vibration upon complexation. It is suggested that the blue-shift is a normal effect for these molecules, and that originates from the enhanced (HNg)+Y- ion-pair character upon complexation. It is also found that the HNgY molecules are energetically stabilized in the complexed form, and this effect is computationally demonstrated for the HHeF molecule. The NgHNg+ and YHY- ions also show blue-shifts in their asymmetric stretching vibration upon complexation with nitrogen. Additionally, the matrix site structure and hindered rotation (libration) of the HNgY molecules were studied. The librational motion is a much-discussed solid state phenomenon, and the HNgY molecules embedded in noble-gas matrices are good model systems to study this effect. The formation mechanisms of the HNgY molecules and the decay mechanism of NgHNg+ cations are discussed. A new electron tunneling model for the decay of NgHNg+ absorptions in noble-gas matrices is proposed. Studies of the NgHNg+∙∙∙N2 complexes support this electron tunneling mechanism.

On the valence state of molybdenum in Ce2MoO6

The valence state of molybdenum in cubic Ce2MoO6 was investigated using magnetic susceptibility measurements, electron spin resonance spectroscopy and X-ray absorption spectroscopy. The results are consistent with the formulation Ce3+Ce4+Mo5+O6.

Experimental investigation of catalytic and non-catalytic surface reactions on SiO2 thin films with shock heated oxygen gas

The present study is to investigate the interaction of strong shock heated oxygen on the surface of SiO2 thin film. The thermally excited oxygen undergoes a three-body recombination reaction on the surface of silicon dioxide film. The different oxidation states of silicon species on the surface of the shock-exposed SiO2 film are discussed based on X-ray Photoelectron Spectroscopy (XPS) results. The surface morphology of the shock wave induced damage at the cross section of SiO2 film and structure modification of these materials are analyzed using scanning electron microscopy and ion microscopy. Whether the surface reaction of oxygen on SiO2 film is catalytic or non-catalytic is discussed in this paper.

A Convenient Route for the Synthesis of Complex Metal Oxides Employing Solid-Solution Precursors

Synthesis of complex metal oxides by the thermal decomposition of solid-solution precursors (formed by isomorphous compounds of component metals) has been investigated since the method enables mixing of cations on an atomic scale and drastically reduces diffusion distances to a few angstroms. Several interesting oxides such as Ca2Fe03,5C, aCoz04,C a2C0205a, nd Ca,FeCo05 have been prepared by this technique starting from carbonate solid solutions of the type Ca,-,Fe,C03, Cal-,Co,C03, and Ca,-,,M,M'yC03 (M, M' = Mn, Fe, Co). The method has been extended to oxalate solid-solution precursors, and the possibility of making use of other kinds of precursor solid solutions is indicated.

Conformational characterisation of valinomycin complexation with barium salts:A nuclear magnetic resonance spectroscopic study

Conformations of valinomycin and its complexes with Perchlorate and thiocyanate salts of barium, in a medium polar solvent acetonitrile, were studied using nuclear magnetic resonance spectroscopic techniques. Valinomycin was shown to have a bracelet conformation in acetonitrile. With the doubly charged barium ion, the molecule, at lower concentrations, predominantly formed a 1:1 complex. At higher concentrations, however, apart from the 1:1, peptide as well as ion sandwich complexes were formed in addition to a :final complex:. Unlike the standard 1:1 potassium complex, where the ion was centrally located in a bracelet conformation, the a 1:1 barium complex contained the barium ion at the periphery. The a :final complex: appeared to be an open conformation with no internal hydrogen bonds and has two bound barium ions. This complex was probably made of average of many closely related conformations that were exchanging very fast (on nuclear magnetic resonance time scale) among them. The conformation of the a:final complex a: resembled the conformation obtained in the solid state. Unlike the Perchlorate anion, the thiocyanate anion seemed to have a definite role in stabilising the various complexes. While the conformation of the 1:1 complex indicated a mechanism of ion capture at the membrane interface, the sandwich complexes might explain the transport process by a relay mechanism.

Itinerant electron ferromagnetism in Sr2+-, Ca2+-, and Ba2+-doped rare-earth orthocobaltites (Ln3+1�xM2+xCoO3)

Electronic and magnetic properties of Ln1�xSrxCoO3 (Ln = Pr, Nd, Sm, Eu, and Gd) systems show that above a critical value of x, the d electrons become itinerant while the materials become ferromagnetic at low temperatures. The ferromagnetic component increases with increase in x and decrease in temperature. The Curie temperature increases with x and decreases with decrease in the size of the rare-earth ion. Incorporation of Ba2+ in LaCoO3 favors itinerant electron ferromagnetism relative to Sr2+ while Ca2+ is less favorable than Sr2+.

Metal-insulator transition of naxwo3 studied by angle-resolved photoemission spectroscopy

The electronic structure of sodium tungsten bronzes NaxWO3 is investigated by high-resolution angle-resolved photoemission spectroscopy (ARPES). The ARPES spectra measured in both insulating and metallic phases of NaxWO3 reveals the origin of metal-insulator transition (MIT) in sodium tungsten bronze system. It is found that in insulating NaxWO3 the states near the Fermi level (E-F) are localized due to the strong disorder caused by the random distribution of Na+ ions in WO3 lattice. Due to the presence of disorder and long-range Coulomb interaction of conduction electrons, a soft Coulomb gap arises, where the density of states vanishes exactly at E-F. In the metallic regime the states near E-F are populated and the Fermi level shifts upward rigidly with increasing electron doping (x). Volume of electron-like Fermi surface (FS) at the Gamma(X) point of the Brillouin zone gradually increases with increasing Na concentration due to W 5d t(2g) band filling. A rigid shift of the Fermi energy is found to give a qualitatively good description of the Fermi surface evolution. As we move from bulk-sensitive to more surface sensitive photon energy, we found the emergence of Fermi surfaces at X(M) and M(R) point similar to the one at the Gamma(X) point in the metallic regime, suggesting that the reconstruction of surface was due to rotation/deformation of WO6 octahedra.

Ferromagnetic resonance in Sr2+ doped rare earth orthocobaltites, Ln1â xSrxCoO3

FMR measurements have been carried out on several members of the Ln1âxSrxCoO3 (Ln = Rare earth) system. The results show that geff in these systems is around 1.25 independent of x as well as the rare earth ion. It is suggested that this unusual value of geff is due to the localized intermediate-spin Co3+ ions (t52ge1g) located at the top of the Ï* band.

High Lithium Storage in Mixed Crystallographic Phase Nanotubes of Titania and Carbon-Titania

Morphology and electrochemical performance of mixed crystallographic phase titania nanotubes for prospective application as anode in rechargeable lithium ion batteries are discussed. Hydrothermally grown nanotubes of titania (TiO2) and carbon-titania (C-TiO2) comprise a mixture of both anatase and TiO2 (B) crystallographic phases. The first cycle capacity (at Current rate = 10 mAg(-1)) for bare TiO2 nanotubes was 355 mAhg(-1) (approximately 1.06 Li), which is higher than both the theoretical capacity (335 mAhg(-1)) and the reported values for pure anatase and TiO2 (B) nanotubes. Higher capacity is attributed to it combination of the presence of mixed crystallographic phases of titania and trivial size effects. The surface area of bare TiO2 nanotubes was very high at 340 m(2) g(-1). C-TiO2 nanotubes showed a slightly lower first-cycle specific capacity of 307 mAhg(-1), but the irreversible capacity loss in the first cycle decreased by half compared to bare TiO2 nanotubes. The C-TiO2 nanotubes also showed a better rate capability, that is, higher capacities compared to bare TiO2 nanotubes in the Current range 0.1-2 Ag-1. Enhanced rate capability in the case of C-TiO2 is attributed to the efficient percolation of electrons as well its to the decrease in the anatase phase.

Diffusion of localized optical excitations and trap emission in ruby

Using the critical percolation conductance method the energy-dependent diffusion coefficient associated with thermally assisted transfer of the R1 line excitation between single Cr3+ ions with strain-induced randomness has been calculated in the 4A2 to E(2E) transition energies. For localized states sufficiently far away from the mobility edge the energy transfer is dominated by dipolar interactions, while very close to the mobility edge it is determined by short-range exchange interactions. Using the above energy-dependent diffusion coefficient a macroscopic diffusion equation is solved for the rate of light emission by Cr3+ ion-pair traps to which single-ion excitations are transferred. The dipolar mechanism leads to good agreement with recent measurements of the pair emission rate by Koo et al. (Phys. Rev. Lett., vol.35, p.1669 (1975)) right up to the mobility edge.