ELECTROCATALYTIC PROPERTIES OF MIXED-VALENCE MOLYBDENUM OXIDE THIN-FILM MODIFIED MICROELECTRODES

A compact blue conducting mixed-valence Mo (VI,V) oxide film was grown on the surface of a carbon fibre (CF) microelectrode by cycling the potential between +0.20 and similar to 0.70 V SCE in freshly prepared Na2MoO4 solution in H2SO4 (pH 2). The thicknes

Remarkable stability of ionic gold supported on sulfated lanthanum oxide

Isolated cationic gold deposited on sulfated lanthanum oxide has been shown to exhibit remarkable stability opening a promising way of stabilising ionic gold for catalytic reactions.

Fabrication of cerium oxide nanoparticles: Characterization and optical properties

Ceria (CeO2) is a technologically important rare earth material because of its unique properties and various engineering and biological applications. A facile and rapid method has been developed to prepare ceria nanoparticles using microwave with the average size 7 nm in the presence of a set of ionic liquids based on the bis (trifluoromethylsulfonyl) imide anion and different cations of 1-alkyl-3-methyl-imidazolium. The structural features and optical properties of the nanoparticles were determined in depth with X-ray powder diffraction, transmission electron microscope, N-2 adsorption-desorption technique, dynamic light scattering (DLS) analysis, FTIR spectroscopy, Raman spectroscopy, UV-vis absorption spectroscopy, and Diffuse reflectance spectroscopy. The energy band gap measurements of nanoparticles of ceria have been carried out by UV-visible absorption spectroscopy and diffuse reflectance spectroscopy. The surface charge properties of colloidal ceria dispersions in ethylene glycol have been also studied. To the best of our knowledge, this is the first report on using this type of ionic liquids in ceria nanoparticle synthesis. (C) 2011 Elsevier Inc. All rights reserved.

Thin catalytic coatings on microreactor walls A way to make industrial processes more efficient

Current trends in the development of microstructured reactors with thin catalytic films (from 100 nm up to several microns) that have self-assembled nanostructures are discussed. A major technique that is used to prepare such films is sol-gel processing. This involves depositing a complex fluid on a microstructured substrate by dip, spin, or spray coating, followed by surfactant removal to form the porous nanostructures. A novel methodology has been developed by which a uniform coating containing controlled amounts of (poly) metallic nanoparticles can be obtained. This elegant strategy is based on the condensation of metal oxide species by self-assembly in the presence of metallic colloids. The potential microreactor applications brought forth by this innovative protocol are placed in perspective in the light of its versatility.

Phosphine oxide functionalised imidazolium ionic liquids as tuneable ligands for lanthanide complexation

A series of novel, phosphine oxide functionalised ionic liquids have been synthesised and their application as tuneable lanthanide complexing agents is demonstrated.

A computational study of the mechanism of CO oxidation by a ceria supported surface rhodium oxide layer

A mechanism of CO oxidation by a thin surface oxide of Rh supported on ceria is proposed: CO is oxidized by the Rh-oxide film, which is subsequently reoxidized by a ceria surface O atom. The proposed mechanism is supported by in situ Raman spectroscopic investigations.

A Microscopic Study of Iron and Manganese Oxide Distribution in Soils from East Tennessee (U.S.A.)

Soils and saprolites developed from interbedded shales and limestones of the Conasauga Group are widespread in the Valley and Ridge Province of East Tennessee. Thin sections from four soil profiles were examined by petrographic and scanning electron microscopy including backscatter electron and energy-dispersive X-ray analyses. Iron and manganese released by weathering had migrated differentially downward and precipitated as crystalline and noncrystalline oxides. Oxides were observed as nodules, granular particulates, pore fillings, and coatings on other minerals, packing voids, vesicles, channels, and chambers. Iron oxides formed predominantly as coatings on packing-void walls and on laminated clays in vesicles and channels. Manganese oxides occurred as an early replacement phase of packing voids and of fracture-filling carbonate minerals. Iron oxides were dominant in moderately well-drained and oxidized horizons of the soil solum, whereas manganese oxides were abundant in the oxidized and moderately leached saprolite zone where the water table fluctuates seasonally. Therefore, a manganese enrichment zone, on a bulk soil basis, occurred generally below the iron oxide zone in the soil profile. Such differential migration and accumulation of iron and manganese have been controlled by localized soil microenvironments. Micromorphologic features observed in this study are important in land-use evaluation for hazardous waste disposal. © 1990.

High temperature thermal stability studies of ultrathin Al2O3 layers deposited on native oxide and sulphur passivated InGaAs surfaces

High resolution synchrotron radiation core level photoemission measurements have been used to undertake a comparative study of the high temperature stability of ultrathin Al2O3 layers deposited by atomic layer deposition (ALD) on both sulphur passivated and native oxide covered InGaAs. The residual interfacial oxides between sulphur passivated InGaAs and the ultrathin Al2O3 layer can be substantially removed at high temperature (up to 700 °C) without impacting on the InGaAs stoichiometry while significant loss of indium was recorded at this temperature on the native oxide InGaAs surface.

Chemical vapour deposition of vanadium oxide thermochromic thin films

Thermochromic materials change optical properties, such as transmittance or reflectance, with a variation in temperature. An ideal intelligent (smart) material will allow solar radiation in through a window in cold conditions, but reflect that radiation in warmer conditions. The variation in the properties is often associated with a phase change, which takes place at a definite temperature, and is normally reversible. Such materials are usually applied to window glass as thin films. This thesis presents the work on the development of thermochromic vanadium (IV) oxide (VO2) thin films – both undoped and doped with tungsten, niobium and gold nanoparticles – which could be employed as solar control coatings. The films were deposited using Chemical Vapour Deposition (CVD), using improved Atmospheric Pressure (APCVD), novel Aerosol Assisted (AACVD) and novel hybrid AP/AACVD techniques. The effects of dopants on the metalto- semiconductor transition temperature and transmittance/reflectance characteristics were also investigated. This work significantly increased the understanding of the mechanisms behind thermochromic behaviour, and resulted in thermochromic materials based on VO2 with greatly improved properties.

Lanthanide oxide and phosphate nanoparticles for thermometry and bimodal imaging

Nesta tese relatam-se estudos de fotoluminescência de nanopartículas de óxidos e fosfatos dopados com iões trivalentes de lantanídeos, respectivamente, nanobastonetes de (Gd,Eu)2O3 e (Gd,Yb,Er)2O3 e nanocristais de (Gd,Yb,Tb)PO4, demonstrando-se também aplicações destes materiais em revestimentos inteligentes, sensores de temperatura e bioimagem. Estuda-se a transferência de energia entre os sítios de Eu3+ C2 e S6 dos nanobastonetes Gd2O3. A contribuição dos mecanismos de transferência de energia entre sítios para o tempo de subida 5D0(C2) é descartada a favor da relaxação directa 5D1(C2) 5D0(C2) (i.e., transferência de energia entre níveis). O maior tempo de decaimento do nível 5D0(C2) nos nanobastonetes, relativamente ao valor medido para o mesmo material na forma de microcristais, é atribuído, quer à existência de espaços livres entre nanobastonetes próximos (factor de enchimento ou fracção volúmica), quer à variação do índice de refracção efectivo do meio em torno dos iões Eu3+. A dispersão de nanobastonetes de (Gd,Eu)2O3 em três resinas epoxi comerciais através da cura por UV permite obter nanocompósitos epoxi- (Gd,Eu)2O3. Relatam-se estudos cinéticos e das propriedades térmicas e de fotoluminescência destes nanocompósitos. Estes, preservam as típicas propriedades de emissão do Eu3+, mostrando o potencial do método de cura por UV para obter revistimentos inteligentes e fotoactivos. Considera-se um avanço significativo a realização de uma nanoplataforma óptica, incorporando aquecedor e termómetro e capaz de medir uma ampla gama de temperaturas (300-2000 K) à escala nano, baseada em nanobastonetes de (Gd,Yb,Er)2O3 (termómetros) cuja superfície se encontra revestida com nanopartículas de ouro. A temperature local é calculada usando, quer a distribuição de Boltzmann (300-1050 K) do rácio de intensidades da conversão ascendente 2H11=2!4I15=2/4S3=2!4I15=2, quer a lei de Planck (1200-2000 K) para uma emissão de luz branca atribuída à radiação do corpo negro. Finalmente, estudam-se as propriedades de fotoluminescência correspondentes às conversões ascendente e descendente de energia em nanocristais de (Gd,Yb,Tb)PO4 sintetizados por via hidrotérmica. A relaxividade (ressonância magnética) do 1H destes materiais são investigadas, tendo em vista possíveis aplicações em imagem bimodal (luminescência e ressonância magnética nuclear).

Spray Pyrolysed Zinc Oxide Thin Films : Effects of Doping and Ion Beam Irradiation

In recent years scientists have made rapid and significant advances in the field of semiconductor physics. One of the most important fields of current interest in materials science is the fundamental aspects and applications of conducting transparent oxide thin films (TCO). The characteristic properties of such coatings are low electrical resistivity and high transparency in the visible region. The first semitransparent and electrically conducting CdO film was reported as early as in 1907 [1]. Though early work on these films was performed out of purely scientific interest, substantial technological advances in such films were made after 1940. The technological interest in the study of transparent semiconducting films was generated mainly due to the potential applications of these materials both in industry and research. Such films demonstrated their utility as transparent electrical heaters for windscreens in the aircraft industry. However, during the last decade, these conducting transparent films have been widely used in a variety of other applications such as gas sensors [2], solar cells [3], heat reflectors [4], light emitting devices [5] and laser damage resistant coatings in high power laser technology [6]. Just a few materials dominate the current TCO industry and the two dominant markets for TCO’s are in architectural applications and flat panel displays. The architectural use of TCO is for energy efficient windows. Fluorine doped tin oxide (FTO), deposited using a pyrolysis process is the TCO usually finds maximum application. SnO2 also finds application ad coatings for windows, which are efficient in preventing radiative heat loss, due to low emissivity (0.16). Pyrolitic tin oxide is used in PV modules, touch screens and plasma displays. However indium tin oxide (ITO) is mostly used in the majority of flat panel display (FPD) applications. In FPDs, the basic function of ITO is as transparent electrodes. The volume of FPD’s produced, and hence the volume of ITO coatings produced, continues to grow rapidly. But the current increase in the cost of indium and the scarcity of this material created the difficulty in obtaining low cost TCOs. Hence search for alternative TCO materials has been a topic of active research for the last few decades. This resulted in the development of binary materials like ZnO, SnO2, CdO and ternary materials like II Zn2SnO4, CdSb2O6:Y, ZnSO3, GaInO3 etc. The use of multicomponent oxide materials makes it possible to have TCO films suitable for specialized applications because by altering their chemical compositions, one can control the electrical, optical, chemical and physical properties. But the advantages of using binary materials are the easiness to control the chemical compositions and depositions conditions. Recently, there were reports claiming the deposition of CdO:In films with a resistivity of the order of 10-5 ohm cm for flat panel displays and solar cells. However they find limited use because of Cd-Toxicity. In this regard, ZnO films developed in 1980s, are very useful as these use Zn, an abundant, inexpensive and nontoxic material. Resistivity of this material is still not very low, but can be reduced through doping with group-III elements like In, Al or Ga or with F [6]. Hence there is a great interest in ZnO as an alternative of ITO. In the present study, we prepared and characterized transparent and conducting ZnO thin films, using a cost effective technique viz Chemical Spray Pyrolysis (CSP). This technique is also suitable for large area film deposition. It involves spraying a solution, (usually aqueous) containing soluble salts of the constituents of the desired compound, onto a heated substrate.

Growth and Characterisation of Radio Frequency Magnetron Sputttered Indium Tin Oxide Thin Films

The increasing interest in the interaction of light with electricity and electronically active materials made the materials and techniques for producing semitransparent electrically conducting films particularly attractive. Transparent conductors have found major applications in a number of electronic and optoelectronic devices including resistors, transparent heating elements, antistatic and electromagnetic shield coatings, transparent electrode for solar cells, antireflection coatings, heat reflecting mirrors in glass windows and many other. Tin doped indium oxide (indium tin oxide or ITO) is one of the most commonly used transparent conducting oxides. At present and likely well into the future this material offers best available performance in terms of conductivity and transmittivity combined with excellent environmental stability, reproducibility and good surface morphology. Although partial transparency, with a reduction in conductivity, can be obtained for very thin metallic films, high transparency and simultaneously high conductivity cannot be attained in intrinsic stoichiometric materials. The only way this can be achieved is by creating electron degeneracy in a wide bandgap (Eg > 3eV or more for visible radiation) material by controllably introducing non-stoichiometry and/or appropriate dopants. These conditions can be conveniently met for ITO as well as a number of other materials like Zinc oxide, Cadmium oxide etc. ITO shows interesting and technologically important combination of properties viz high luminous transmittance, high IR reflectance, good electrical conductivity, excellent substrate adherence and chemical inertness. ITO is a key part of solar cells, window coatings, energy efficient buildings, and flat panel displays. In solar cells, ITO can be the transparent, conducting top layer that lets light into the cell to shine the junction and lets electricity flow out. Improving the ITO layer can help improve the solar cell efficiency. A transparent ii conducting oxide is a material with high transparency in a derived part of the spectrum and high electrical conductivity. Beyond these key properties of transparent conducting oxides (TCOs), ITO has a number of other key characteristics. The structure of ITO can be amorphous, crystalline, or mixed, depending on the deposition temperature and atmosphere. The electro-optical properties are a function of the crystallinity of the material. In general, ITO deposited at room temperature is amorphous, and ITO deposited at higher temperatures is crystalline. Depositing at high temperatures is more expensive than at room temperature, and this method may not be compatible with the underlying devices. The main objective of this thesis work is to optimise the growth conditions of Indium tin oxide thin films at low processing temperatures. The films are prepared by radio frequency magnetron sputtering under various deposition conditions. The films are also deposited on to flexible substrates by employing bias sputtering technique. The films thus grown were characterised using different tools. A powder x-ray diffractometer was used to analyse the crystalline nature of the films. The energy dispersive x-ray analysis (EDX) and scanning electron microscopy (SEM) were used for evaluating the composition and morphology of the films. Optical properties were investigated using the UVVIS- NIR spectrophotometer by recording the transmission/absorption spectra. The electrical properties were studied using vander Pauw four probe technique. The plasma generated during the sputtering of the ITO target was analysed using Langmuir probe and optical emission spectral studies.

Aqueous Sol-gel Process for Nanocrystalline Photocatalytic Titania, Transparent Functional Coatings and Ceramic Membrane

The present thesis develops from the point of view of titania sol-gel chemistry and an attempt is made to address the modification of the process for better photoactive titania by selective doping and also demonstration of utilization of the process for the preparation of supported membranes and self cleaning films.A general introduction to nanomaterials, nanocrystalline titania and sol-gel chemistry are presented in the first chapter. A brief and updated literature review on sol-gel titania, with special emphasis on catalytic and photocatalytic properties and anatase to rutile transformation are covered. Based on critical assessment of the reported information the present research problem has been defined.The second chapter describes a new aqueous sol-gel method for the preparation of nanocrystalline titania using titanyl sulphate as precursor. This approach is novel since no earlier work has been reported in the same lines proposed here. The sol-gel process has been followed at each step using particle size, zeta potential measurements on the sol and thermal analysis of the resultant gel. The prepared powders were then characterized using X-ray diffraction, FTIR, BET surface area analysis and transmission electron microscopy.The third chapter presents a detailed discussion on the physico-chemical characterization of the aqueous sol-gel derived doped titania. The effect of dopants such as tantalum, gadolinium and ytterbium on the anatase to rutile phase transformation, surface area as well as their influence on photoactivity is also included. The fourth chapter demonstrates application of the aqueous sol-gel method in developing titania coatings on porous alumina substrates for controlling the poresize for use as membrane elements in ultrafiltration. Thin coatings having ~50 nm thickness and transparency of ~90% developed on glass surface were tested successfully for self cleaning applications.

Nanostructured europium oxide thin films deposited by pulsed laser ablation of a metallic target in a He buffer atmosphere

Nanostrucured europium oxide and hydroxide films were obtained by pulsed Nd:YAG (532 nm) laser ablation of a europium metallic target, in the presence of a 1 mbar helium buffer atmosphere. Both the produced film and the ambient plasma were characterized. The plasma was monitored by an electrostatic probe, for plume expansion in vacuum or in the presence of the buffer atmosphere. The time evolution of the ion saturation current was obtained for several probe to substrate distances. The results show the splitting of the plume into two velocity groups, being the lower velocity profile associated with metal cluster formation within the plume. The films were obtained in the presence of helium atmosphere, for several target-to-substrate distances. They were analyzed by Rutherford backscattering spectrometry, x-ray diffraction, and atomic force microscopy, for as-deposited and 600 degrees C treated-in-air samples. The results show that the as-deposited samples are amorphous and have chemical composition compatible with europium hydroxide. The thermally treated samples show x-ray diffraction peaks of Eu(2)O(3), with chemical composition showing excess oxygen. Film nanostructuring was shown to be strongly correlated with cluster formation, as shown by velocity splitting in probe current versus time plots. (C) 2010 American Vacuum Society. [DOI: 10.1116/1.3457784]

A statistical evaluation of the field emission for copper oxide nanostructures

A statistical data analysis methodology was developed to evaluate the field emission properties of many samples of copper oxide nanostructured field emitters. This analysis was largely done in terms of Seppen-Katamuki (SK) charts, field strength and emission current. Some physical and mathematical models were derived to describe the effect of small electric field perturbations in the Fowler-Nordheim (F-N) equation, and then to explain the trend of the data represented in the SK charts. The field enhancement factor and the emission area parameters showed to be very sensitive to variations in the electric field for most of the samples. We have found that the anode-cathode distance is critical in the field emission characterization of samples having a non-rigid nanostructure. (C) 2007 Elsevier B.V. All rights reserved.