Polymer dye-containing nanocomposites as photocatalysts

A significant improvement of photocatalytic efficiency is achieved by the synthesis of TiO₂/SiO₂ nanocomposites where silica matrix provides the transport of reagents to TiO₂ nanoparticles via porous structure, generation of the new active sites and thermal stability. The semiconductive films contained 10 or 30% of TiO₂ in silica matrix are synthesized by sol-gel method using concentrated anatase titania colloid. The complex composites consisted of i) the Acridine Yellow dye molecules and the polyepoxypropyl carbazole; ii) the azobenzene containing polymer covered onto the titania/silica films are obtained as photocatalytic materials. Photocatalytic activity of the composites is tested via the reduction of dichromate ions.     

Mixed metal oxide nanocomposites derived from layered double hydroxides as photocatalysts for C.I. Basic Blue 3 degradation under UV light

In this research we report synthesis of the heterostructure Mg‐Al‐Zn mixed metal oxide (ZnO/MMO) nanocomposite photocatalysts derived from Zn(OH)₂/Mg‐Al‐layered double hydroxides (ZLDHs) precursors. The obtained samples were characterized by the X‐ray diffraction (XRD), FT‐IR, BET surface area, ICP and TG/DTG methods. The chemical compositions and morphology of the synthesized materials were investigated by the energy dispersive X‐ray analysis (EDX) and the transmission electron microscopy (TEM). The results reveal that at the reaction time 96 h, ZLDH has the highest crystalinity which was confirmed by the X‐ray diffraction spectra. The calcined samples at 500, 600 and 700 °C for 4 h show that the crystallinity of the nanocomposite improves with the increase of calcination temperature. The photocatalytic activities of synthesized nanocomposites were compared for the degradation of C. I. Basic Blue 3 (BB3) dye under UV illumination in aqueous solution. Among the synthesized nanocomposites, ZnO/MMO calcined at 700 °C shows the highest efficiency towards the removal of dye. The effect of UV illumination on the stability of ZnO in ZnO/MMO nanocomposite and pure ZnO was also investigated. The results showed that the photostability of ZnO in ZnO/MMO nanocomposite is increased compared to the pure ZnO.     

Amorphous iron-chromium oxide nanoparticles prepared by sonochemistry

Amorphous Fe₂O₃ and Fe_1.9Cr_0.1O₃ materials have been prepared by sonochemical method. X-ray diffraction patterns, transmission electron microscopy, Raman and infrared spectra, differential scanning calorimetry, Mössbauer and magnetic measurements revealed many interesting behaviors of the samples. Reaction to form the materials only occurred at the preparation temperatures of 70 °C or above. Upon heating, the sample prepared at 70°C presented a strong ferromagnetic behavior due to the presence of the magnetite phase coexisting with the hematite phase whereas the samples prepared at higher temperatures presented only the existence of the hematite phase. Thermal analyses of the sample prepared at 80°C revealed three exothermic peaks which were corresponding to the phase changes of dehydroxylation, crystallization of the maghemite phase and maghemite–hematite transition, respectively. The activation energies of the phase changes deduced from the thermal analyses showed that the presence of Cr enhanced the activation energy which can slow down the ageing effect of the amorphous state when being used in practice.     

Low-temperature electron paramagnetic resonance in silver-iron oxide nanoparticles

Water in oil microemulsion technique has been used to obtain silver nanoparticles with a mean size of 7 nm surrounded by a matrix of 2 nm γ-Fe₂O₃ nanoparticles. Magnetic measurements of the sample exhibit a cusp in the ZFC curve at 50 K, which corresponds to the blocking temperature. A detailed study of the thermal evolution of EPR spectra has been performed in the samples. It has been shown that the linewidth, the resonance field and the intensity of the EPR line show different behaviour near the blocking temperature.     

Investigations on Sn-doped Ni oxide thin films and their use as optical sensor devices

Tin-doped NiO thin films (5.0, 7.4, and 9.3 at.% Sn) have been prepared by thermal oxidation of vacuum deposited films of pure Ni and Sn elements on glass and silicon substrates. The prepared films were comprehensively characterised by X-ray fluorescence, X-ray diffraction, UV–VIS-NIR absorption spectroscopy, and electrical (ac and dc) measurements. Experimental data indicate that Sn⁴⁺ doping slightly stress the host NiO crystalline structure and change the optical and electrical properties. The electrical and optical behaviours of the Sn-doped NiO films show that they are wide-band semiconductors with band gap 3.69–3.76 eV and have insulating properties. The ac and dc electrical measurements show that it is possible to use Sn-doped NiO as an optical-sensitive oxide in metal-oxide-silicon configurations.     

Temperature evolution of copper oxide nanoparticles in porous glasses

The temperature evolution of copper oxide nanoparticles in the temperature range of 1.5–250 K has been investigated by thermal-neutron diffraction. CuO particles were obtained by Cu(NO₃)₂ · 3H₂O decomposition directly in the pores of porous glass with an average pore diameter of 7 nm. The characteristic nanoparticle size and linear thermal expansion coefficients have been determined.     

Effect of citric acid and starch as emulsifier on phase formation and crystallite size of lanthanum oxide nanoparticles

Lanthanum oxide nanoparticles were synthesized via thermal decomposition method of the lanthanum nitrate in the presence of citric acid or starch as emulsifier. The effects of emulsifier and calcination temperature were investigated on the phase transformation and particle size distribution of the products. La₂O₃ nanoparticles were synthesized by drying lanthanum precursor and emulsifier solution, followed by calcination process at 600 and 900°C, respectively. Products were characterized by Fourier Transform Infrared (FT‐IR) spectroscopy, X‐ray diffraction (XRD), thermal analysis (TG/DTA) and nitrogen adsorption method (porous characteristics). The morphology of the samples analyzed using scanning electron microscopy (SEM). Average crystallite size of the products was calculated by XRD data and average particle size was measured from the TEM micrographs. Lanthanum dioxycarbonate in different forms of the tetragonal and monoclinic is crystallized in the presence of citric acid and starch during the calcination at 600°C, respectively. The hexagonal structure, however, is detected as the only crystalline phase formed by calcination at 900°C.     

Synthesis, properties, and applications of magnetic iron oxide nanoparticles

Magnetic nanoparticles exhibit many interesting properties that can be exploited in a variety of applications such as catalysis and in biomedicine. This review discusses the properties, applications, and syntheses of three magnetic iron oxides – hematite, magnetite, and maghemite – and outlines methods of preparation that allow control over the size, morphology, surface treatment and magnetic properties of their nanoparticles. Some challenges to further development of these materials and methods are also presented.     

Electron crystallography as an informative method for studying the structure of nanoparticles

The overwhelming majority of modern nanotechnologies deal with nanoparticles owing to the great variety of their unusual properties, which make them irreplaceable in various fields of science and technology. Since the physical properties of nanoparticles depend on their composition, structure, and shape, the problem of monitoring these parameters both after and during formation of nanoparticles is very important. Methods of electron crystallography are most informative and appropriate for studying and monitoring nanoparticle parameters. In this review, we briefly report the main modern methods based on the use of electron diffraction and electron microscopy, along with examples of their applications for nanoparticles, to solve a number of urgent structural problems of nanomaterials science.     

High performance visible light responsive photocatalysts for environmental cleanup via solution processing

Fabrication of nitrogen-doped titania and/or strontium titanate nanoparticles via soft chemical reactions and their performance for environmental cleanup under visible light irradiation were introduced. Nitrogen-doped anatase, brookite and rutile with high specific surface area can be selectively prepared by the solvothermal reactions in mixed aqueous solution of titanium trichloride-hexamethylenetetramine. Nitrogen-doped strontium titanate can be prepared by mechanochemical reaction of strontium carbonate, titania and hexamethylenetetramine using a planetary ball-mill. Nitrogen-doped titania shows excellent photocatalytic activity for the nitrogen monoxide destruction under visible light irradiation. The photocatalytic activity of nitrogen-doped titania is in the order anatase > brookite > rutile. The photocatalytic activity of nitrogen-doped titania and strontium titanate can be improved by co-doping with higher valence metal ions to reduce oxygen vacancy and/or coupling with Fe₂O₃ and Pt to retard quick recombination of photo-induced electron and hole by the heterogeneous electron transfer.     

Magnetic and structural characterization of silver-iron oxide nanoparticles obtained by the microemulsion technique

In the present paper we report the magnetic characterization of silver-iron oxide nanocomposite obtained by the chemical microemulsion method. TEM images and X-ray diffractograms show that the nanocomposite consists of Ag nanoparticles of ～ 7 nm surrounded by a quasiamorphous matrix. The ZFC–FC curves and Mössbauer spectra obtained at different temperatures show a typical evolution of a system composed of weakly interacting nanoparticles with a blocking temperature (T_b) of ～50 K. The analysis of the magnetic data reveals that the matrix is formed by γ-Fe₂O₃ phase with a structural range order of ～2 nm.     

Low temperature deposition of zinc oxide nanoparticles via zinc-rich vapor phase transport and condensation

ZnO nanoparticles as small as 80 nm were successfully synthesized using a modified vapor phase transport (VPT) process at substrate temperatures as low as 222 °C. Particle size distribution and morphology were characterized by scanning electron microscopy and atomic force microscopy. Energy dispersive X-ray spectroscopy and X-ray diffraction indicate the synthesis of high quality crystalline ZnO structures. Low temperature (4.2 K) photoluminescence (PL) spectroscopy was used to characterize the optical quality of the nanoparticles. Ultraviolet emission and a nanostructure specific feature at 3.366 eV are strong in the PL spectra. The 3.366 eV feature is observed to predominate the spectrum with decrease in particle size. This size effect corroborates the luminescence as a nanostructure-specific surface related exciton feature as previously speculated in the literature. In addition, self-assembled ZnO mesoparticles (>100 nm) were realized by increasing the growth time. Low growth temperatures of the particles allow for their potential utilization in flexible organic hybrid optoelectronics. However, this work focuses mainly on the modified synthesis and optical characterization of nanoparticles.     

Controlled continuous hydrothermal synthesis of cobalt oxide (Co3O4) nanoparticles

Cubic Co₃O₄ nanoparticles have been produced hydrothermally by mixing high temperature water (sub-, near to supercritical) with an aqueous cobalt acetate precursor at high pressure. The relationship between operating variables such as synthesis temperature and residence time on particle size and conversion rate was examined. An increasing nanoparticle size was observed when synthesis temperature was increased, particularly in the range from 200 °C to 330 °C. Residence times of 0.5 s and 7 s appeared to strongly influence nanoparticle size while residence time greater than 7 s did not show any significant effect. Increasing reaction temperature or residence time both resulted in higher conversion rates. The Langmuir mathematical equation has been proposed as a kinetic expression that models nanoparticle size versus residence time for various reaction temperatures. The data generated using this model agrees well with experimental results which can be used to predict particle size at any given temperature and/or residence time.     

Investigations of curved graphite crystals for the use as X-ray monochromators

X-ray investigations on curved graphite crystals for focusing monochromators for X-ray powder diffractometers are performed. The reflection power, avertences of crystal blocks, and radius of curvature of these crystals were determined by measuring rocking curves in dependence on the crystal position. The favourable application of curved graphite crystals as monochromators is shown by comparative X-ray measurements of selected reflexes.     

Liquid crystal material with gold nanoparticles as optical sensors active medium for the amino acids detection

Abstract

In the article, the possibility of using the cholesteric liquid crystal mixture doped by the gold nanoparticles as an active medium of optical amino acid sensors is shown. The BLO-62 and the 5CB were used as a cholesteric liquid crystal and a nematic liquid crystal correspondingly. This mixture was doped by the gold nanoparticles. The method of gold nanoparticles synthesis is considered and their parameters are determined. Studies on the spectral characteristics of the investigated materials have shown that the addition of gold nanoparticles to the system leads to a significant decreasing in the spectral characteristic steepness and give the possibility of expanding the measurement range of amino acid concentration.     

A low silica, barium borate glass-ceramic for use as seals in planar SOFCs

A low silica, barium borate glass-ceramic for use as seals in planar SOFCs containing 64 mol%BaO, 3 mol%Al₂O₃ and 3 mol%SiO₂ was studied. Coefficient of thermal expansion (CTE) between 275-550 °C, glass transition temperature (T_g), and dilatometric softening point (T_s) of the parent glass were 11.9 × 10⁻⁶ °C⁻¹, 552 °C, and 558 °C, respectively. Glass-ceramic was produced by devitrification heat treatment at 800 °C for 100 h. It was found that nucleation heat treatment, seeding by 3 wt%ZrO₂ as glass-composite and pulverization affected the amount, size and distribution of crystalline phases. SEM-EDS and XRD results revealed that crystalline phases presented in the devitrified glass-ceramic were barium aluminate (BaAl₂O₄), barium aluminosilicate (BaAl₂Si₂O₈) possibly with boron associated in its crystal structure, and barium zirconate (BaZrO₃). CTE of the devitrified glass-ceramic was in the range of (10.1-13.0) × 10⁻⁶ °C⁻¹. Good adhesion was obtained both in the cases of glass and devitrified glass-ceramic with YSZ and AISI430 stainless steel. Interfacial phenomena between these components were discussed.     

Growth of cubic silicon carbide on oxide using polysilicon as a seed layer for micro-electro-mechanical machine applications

The growth of highly oriented 3C–SiC directly on an oxide release layer, composed of a 20-nm-thick poly-Si seed layer and a 550-nm-thick thermally deposited oxide on a (1 1 1)Si substrate, was investigated as an alternative to using silicon-on-insulator (SOI) substrates for freestanding SiC films for MEMS applications. The resulting SiC film was characterized by X-ray diffraction (XRD) with the X-ray rocking curve of the (1 1 1) diffraction peak displaying a FWHM of 0.115° (414″), which was better than that for 3C–SiC films grown directly on (1 1 1)Si during the same deposition process. However, the XRD peak amplitude for the 3C–SiC film on the poly-Si seed layer was much less than for the (1 1 1)Si control substrate, due to slight in-plane misorientations in the film. Surprisingly, the film was solely composed of (1 1 1) 3C–SiC grains and possessed no 3C–SiC grains oriented along the 3 1 1 and 1 1 0 directions which were the original directions of the poly-Si seed layer. With this new process, MEMS structures such as cantilevers and membranes can be easily released leaving behind high-quality 3C–SiC structures.     

New Insights into the structure of Pd-Au nanoparticles as revealed by aberration-corrected STEM

Bimetallic nanoparticles of Au-Pd find important applications in catalysis. Their catalytic performance is directly related to the structure, alloy formation and variation of composition in the structure. A standard idea is that bimetallic nanoparticles can be either an alloy or a core shell structure. Our group has investigated the structure and composition of Pd-Au nanoparticles by using aberration corrected high angle annular dark field scanning transmission electron microscopy (HAADF-STEM). We reported previously that the nanoparticles are composed of an evenly alloyed inner core, an Au-rich intermediate layer, and a Pd-rich outer shell. The structure is more complicated than what simple models can predict. In this paper we report additional studies of this system wherein by carrying out spectral and chemical analysis (STEM*-EDAX, STEM-EELS) the interface structure can now be better identified and understood. Apart from the three-layered core-shell structures we have also been able to observe in some cases a four-layered core-shell structure as well. The entire core-shell structure is not rigid and there is indeed intercalation of Au-Pd into the other layers as well. In addition we have been able to locate stacking faults present in the nanoparticles. We also address the problem of the interface structure between the layers. By using nanodiffraction we have found that the whole structure of the nanoparticles becomes hcp in contrast to the bulk structure of Au or Pd.     

Prospective evaluation of the use of various materials as matrices for active elements of lasers

Methods of prospective evaluation of the use of various materials as active elements for quantum generators for certain applications are considered. The way of evaluation for all kinds of dielectric crystal lasers with respect to optical quantum generators, applicable in technical designs is given. The influence of material properties on the prospective technical use is considered. The results are summarily analyzed.     

Synthesis of anisotropic gold nanoparticles using xylitol as a dual functional reductant and stabilizer

The morphology of gold nanoparticles was controlled with hydrogentetrachloroaurate (HAuCl₄) and xylitol through a hydrothermal process using xylitol as reducing agent and controlled reagent. The molar ratio of xylitol relative to HAuCl₄, reaction time and temperature played important roles in determining the geometric shape and size of the product. These nanoplates were single crystals with planar width of 80‐500 nm. The formation of nanobelts and two‐dimensional single‐crystal nanosheets is explained by the preferential adsorption of xylitol molecules from the solution onto the {111} planes of Au nuclei. These nanosheets could be used, for example, in gas sensors, in the fabrication of nanodevices and substrate materials, in property studies, and also for inducing hypothermia in tumors. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)