Studies on the Preparation of Magnetic Photocatalysts

A crystalline titanium dioxide coating was deposited onto silica insulated magnetite particles to prepare a stable magnetic photocatalyst. The direct deposition of crystalline titanium dioxide was conducted by aging dispersions of insulated magnetite particles in a titanium sol–gel precursor mixture at 60–90°C. The coating process was found to be influenced by pH, alkoxide precursor concentration, aging time and reaction temperature. A mechanism for the formation of the titanium dioxide coating has been proposed. The photocatalytic performance of the prepared particles was found to be related to the preparation conditions.     

不同干燥法制备纳米TiO2光催化剂的光谱研究

本文分别用常态、超临界乙醇和超临界CO2干燥法干燥钛酸正丁酯的醇凝胶，制备纳米TiO2光催化剂。应用XRD，FTIR，FT－Raman和Fluorescent spectrum(FS)等光谱技术对催化剂进行了表征。以光催化降解罗丹明B为模型反应，比较所得样品光催化活性。实验结果表明，不同干燥方法对催化剂的晶相结构、半导体能带结构、光吸收性能、表面性质及光催化活性均产生显著的影响，用超临界CO2干燥法制备的TiO2光催化剂具有较好的光催化活性。     

Phase transitions in the H+-conducting perovskite ceramics by the quasi-elastic neutron and high-pressure Raman scattering

H⁺-containing lanthanide-doped perovskites A(Ba, Sr etc.)B(Zr, Ce, Ti etc.)O₃ are potential ceramic membranes for fuel cell and medium temperature water electrolysis (300–800 °C). The comparison studies of the hydrated and non-hydrated Yb-doped BaZrO₃ and SrZrO₃ were performed by thermal expansion, medium–high temperature neutron and room-temperature high-pressure Raman scattering. Neutron diffraction and elastic/quasi-elastic studies carried out for BaZrO₃ ceramic show the presence of the protons, their successive diffusion above ∼600 °C, and then their departure above 750 °C (under vacuum). Phase transitions and their modification by proton insertion are discussed. A high-pressure Raman study of SrZrO₃ performed at room temperature in the diamond anvil cell reveals the presence of two pressure-induced phase transitions at about 5 and 22 GPa and confirms that proton insertion modifies the phase transition sequences. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

Characteristics of electrohydrodynamically prepared titanium dioxide films

A titanium dioxide precursor sol flowing through a needle at a flow rate of 10^-10 m³ s^-1 was subjected to an electric field of 4.5 kV to generate droplets in the size range 0.3–6 μm. The droplets were collected on a silicon substrate to form uniformly thick, dense films. Raman spectroscopy, X-ray diffraction, field emission scanning electron microscopy and UV/Vis spectroscopy were used to characterize as-deposited and annealed films. Raman spectra show the annealed films were anatase phase with annealing converting it to the rutile phase. The energy bandgap of the titanium dioxide film annealed to 500 °C shows an indirect bandgap energy of 3.50 eV and a direct bandgap energy of 3.95 eV. PACS 81.15.Rs; 81.07.-b; 78.20.-e; 78.30.-j; 78.67.-n; 78.70.ck     

Application of nmr spectroscopy to determine the thermodynamic characteristics of water bound to OX-50 nanosilica

We have used low-temperature 1H NMR spectroscopy to determine the thermodynamic characteristics of water bound to OX-50 nanosilica (SBET ≈ 50 m2/g) in different media: aqueous, air, chloroform medium, and gaseous methane. We demonstrate the difference between the hydration parameters of silica OX-50 on going from an aqueous suspension to a hydrated powder. We present the water cluster size distributions in the studied systems, calculated from the Gibbs–Thomson equation. We found that the average water cluster size in suspension is considerably larger than the cluster sizes in hydrated powders.     

Spectral analysis of the structure of ultradispersed diamonds

The structure of ultradispersed diamonds (UDD) is studied by spectral methods. The presence of diamond crystal phase in the UDD is found based on x-ray analysis and Raman spectra. The Raman spectra also show sp²-and sp³-hybridized carbon. Analysis of IR absorption spectra suggests that the composition of functional groups present in the particles changes during the treatment. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 4, pp. 524–528, July–August, 2008.     

Linear and nonlinear optical properties of hydrated and dehydrated silica micro-spheres under an electric bias

The linear refractive indices and nonlinear second-order susceptibility of hydrated and dehydrated silica micro-spheres are studied using attenuated total reflectance (ATR) and the second harmonic generation (SHG) method in direct transmission, respectively. A dramatic change of the effective dielectric constant of silica suspension under an electric bias was observed, which is attributed to particle redistribution in the fluid. Dielectric constants of dehydrated silica spheres change slightly under an electric field due to Pockels effect, for which we measure a linear electro-optical coefficient of r₃₃ ∼3.4±0.7 pm/V. The transmission second harmonic generation comes from the third-order susceptibility χ⁽³⁾, which is a coupling of two photons and the electrostatic field induced by the surface –OH charges as characterized by the Gouy-Chapman model. The SH signal from the dehydrated silica vanishes because of the loss of –OH groups on the particle surfaces. Dehydration of silica beads is irreversible. The optical properties of dried silica spheres do not recover their original hydrated state when distilled water is added.     

Electrosynthesis of TiO2 oxide film on ITO substrate and electrochemical comparative study of the oxide with its hydrated gel

Thin TiO₂ films obtained by cathodic electrosynthesis from an acidic aqueous bath containing TiOSO₄, H₂O₂ and KNO₃ on conductive glass indium tin oxide have been physically and electrochemically characterised. Secondary ion mass spectroscopy profile of the crystallised gel after heat treatment at 400 °C shows the presence of TiO₂ with traces of TiO and oxygen. X-ray patterns confirm the presence of anatase nanocrystallites for the annealed film and an amorphous structure for the non-annealed gel. Scattering electron microscopy surface micrographies reveal an opened porous nanostructure of the deposits. Cyclic voltammetry and impedance spectroscopic measurements reveal the different behaviour of the films obtained before and after the annealing, showing an important electrical activity of the non-annealed films. The dependence of capacitance values with potential in the anodic domain of depletion is obviously remarked from impedance plots for both gel and crystal forms of the film, which confirmed the fact that films obtained in this way have n-type properties. The potential of flat band equals −0.6 V/Ag/AgCl in pH range of 6.5 has been estimated according to Mott–Shottky curves for the crystallised oxide; meanwhile, the Mott–Shottky curve for the hydrated gel was nonlinear.     

Study of atmospheric water in gaseous and. liquid state by using combined elastic–Raman. depolarization lidar

A combined elastic–Raman lidar system based on a tripled Nd:YAG laser is used for the separate detection of elastic backscatter and Raman signals from atmospheric nitrogen, water vapor and liquid water and for their depolarization measurement. Vertical profiles of water-vapor and liquid-water content measured under clear-sky conditions behave differently: inside the boundary layer the ratio of liquid-water to water-vapor Raman backscatters rises with altitude. The depolarization measurements bring additional information about atmospheric scattering. The observed depolarization ratio of the water-vapor Raman signal is about 14%, while for liquid water this ratio varies in the 30–75% range, which exceeds the depolarization of bulk water and is attributed to the water-aerosol effects. Raman contours of water vapor and liquid water are partially overlapped, and bleed-through of liquid-water Raman backscatter leads to enhancement of depolarization of the water-vapor Raman signal. This parameter may be used as a convenient indicator of liquid-water interference in water-vapor measurements. Received: 12 December 2000 / Revised version: 27 September 2001 / Published online: 7 November 2001     

Influence of drying conditions on the optical and structural properties of sol–gel-derived ZnO nanocrystalline films

Zinc oxide nanothin films were prepared on glass substrate by sol–gel dip-coating method using zinc acetate dihydrate, methanol, and monoethanolamine as precursor, solvent, and stabilizer, respectively. The relationship between drying conditions and the characteristics of ZnO nanocrystalline films (c-axis orientation, grain size, roughness and optical properties) was studied. The films were dried in an oven at different temperatures and by IR radiation. Then, the films were annealed at 500°C in a furnace. The chemical composition, transmission spectra, structure, and morphology of the samples were studied using infrared (IR) and UV–visible spectroscopy, X-ray diffraction (XRD), and atomic force microscopy (AFM), respectively. The XRD results show that the drying conditions affect the orientation of crystallization along the (0 0 2) plane. AFM images show that the thicknesses of the films decrease from 128 to 93 nm by changing the drying conditions. The photoluminescence (PL) of ZnO nanothin films shows the UV emission at near band edge and broad green radiation at about 465 nm wavelength.     

Effect of thermobaric conditions in a uniform bed on the displacement of low-viscosity oil by supercritical carbon dioxide

An experimental setup was constructed that makes it possible to study oil displacement over wide pressure (up to 20 MPa) and temperature (up to 373 K) ranges under conditions reproducing the thermobaric, geological, and physicochemical conditions in real oil beds, as well as the parameters of displacing agents. Experiments on the displacement of kerosene from a model oil bed with supercritical carbon dioxide at temperatures of 313–353 K and pressures within 7–12 MPa were performed. The results are indicative of a high efficiency of recovery of low-viscosity oils with supercritical carbon dioxide.     

Synthesis of α -SiC nanocrystals by carbothermal reduction of spherical nanoparticles of amorphous silicon dioxide

The method for carbothermal reduction of spherical particles of amorphous silicon dioxide is developed, and hexagonal α-SiC polytype nanocrystals are synthesized. The prepared samples are characterized by X-ray diffraction, Raman spectroscopy, photoluminescence spectroscopy, and electron microscopy. The silicon carbide nanocrystals prepared have sizes in the range 5–50 nm depending on the diameter of initial silicon dioxide particles. A detailed analysis of the positions of the lines in the Raman spectra, their broadening, and shift makes it possible to reliably establish that the samples under investigation predominantly contain the 6H and 4H silicon carbide polytypes and insignificant amounts of the 2H and 3C phases. The 15R and 21R polytypes in the samples are absent. It is noted that the samples are characterized by a substantial size effect: the luminescence intensity of small silicon carbide nanocrystals is more than three times higher than that of large SiC nanocrystals.     

Raman characteristics of carbon nitride synthesized by nitrogen-ion-beam-assisted pulsed laser deposition

Raman characteristics of carbon nitride films synthesized by nitrogen-ion-beam-assisted pulsed laser deposition were investigated. In addition to the D (disorder) band and G (graphitic) band commonly observed in carbon nitride films, two Raman bands located at 1080–1100 and 1465–1480 cm^-1 were found from our carbon nitride films. These two bands were well matched with the predicted Raman frequencies for βC₃N₄ and the observed Raman bands reported for carbon nitride films, indicating their relation to carbon-nitrogen stretching vibrations. Furthermore, the relative intensity ratio of the two Raman bands to the D and G bands increased linearly with increasing nitrogen content of the carbon nitride films. Received: 30 October 2000 / Accepted: 5 February 2001 / Published online: 2 October 2001     

Characterization,electrical conduction and stability of Yb-doped barium cerate prepared by sol–gel method

Ceramics powder of BaCe_0.95Yb_0.05O_2.975 was successfully prepared by sol–gel method. Thermogravimetric analysis showed that the decomposition of the dried powder was completed at 1,000 °C. Three strongly exothermic peaks observed in differential thermogravimetric signal indicated three major stages of weight loss in the sample. The high crystallinity of sample with orthorhombic structure was confirmed by X-ray diffraction. The loose particles size obtained from scanning electron microscope was in the range of 65–100 nm, which is almost in the same range as that observed in particle size distribution. The sample showed a dc conductivity of ~1.3 × 10⁻⁴ S cm⁻¹ at 650 °C and the activation energy, E _a, was found to be 1.4 eV. Result of chemical stability test showed that the compound was unstable in atmosphere containing pure carbon dioxide.     

Evolution from vanadium pentoxide xerogel to sodium-containing vanadates in thin films on ITO-coated glasses

In this work, the mechanism of the “gelation” process and the thermal-induced structural modifications of thin film of vanadium pentoxide xerogels deposited on indium tin oxide (ITO)-coated glasses have been studied. Vanadium pentoxide xerogel has been prepared by using the sol–gel proton exchange resin route without any resin pretreatment. To monitor the effect of the “resin efficiency” on the gelation process, the solution coming out from the resin has been collected in a sequence of different containers (vials), separately investigated by Raman spectroscopy. After the spin coating deposition, the thin films of vanadium pentoxide gel have been subjected to different annealing treatments. The highest thermal treatment (600 °C) induces a complete transformation of the gel phase into an anhydrous polycrystalline phase of a sodium-containing vanadate, different from the usual V₂O₅ crystal. It is due to the diffusion of foreign ions (mainly sodium) coming from the substrate into the vanadium oxide layer.     

Narrowing of the vibrational spectrum under compression of liquid carbon dioxide

The broadening and shift of the Q bands of the 1388/1285-cm⁻¹ Fermi doublet of carbon dioxide have been measured by means of the spectroscopy of coherent anti-Stokes Raman scattering in a wide density range realized at compression in dense gaseous and liquid states. The spectrum of the low-frequency Q band exhibits an essential narrowing upon the compression of the liquid in the density range of 320–400 amagat from a maximum width of about 2.2 cm⁻¹ to about 1.7 cm⁻¹ determined by elastic dephasing. The observed dependence is connected with the progressive narrowing of the spectral contribution attributed to the collapsed rotational structure.     

Temperature dependence of the lowest frequency <Emphasis Type="BoldItalic">E</Emphasis><Subscript><Emphasis Type="Bold">g</Emphasis></Subscript> Raman mode in laser-synthesized anatase TiO<Subscript>2</Subscript> nanopowder

Nanosized titanium dioxide (TiO₂) powder was prepared by a laser-induced pyrolysis. Specific surface area of the as-grown powder measured by BET method was 109 m²/g. The grain size (14.5 nm) estimated from these data coincides well with the crystallite size (12.3 nm) determined by XRD measurements. The average grain size (∼35 nm) obtained from the subsequent SEM measurements refers to considerable agglomeration of nanoparticles. Raman spectroscopy has been used to investigate the structural properties of TiO₂ nanopowder and its anatase structure is confirmed. The blueshift and broadening of the lowest frequency E_g Raman mode at temperature range ∼25–550 K have been analyzed using a phonon-confinement model. Dominant influence of the strong anharmonic effect at higher temperatures was demonstrated. PACS 81.07.Wx; 78.30.-j; 63.22.+m     

Adiabatic Raman polariton in a Bose condensate

The Raman interaction of optical fields with a Bose condensate is studied in the adiabatic regime. A superposition of operators is found — one annihilating an atom in a metastable state and the other annihilating a photon in resonance with a transition from the ground state to an excited state — which is an adiabatic invariant of the problem (Raman polariton). Possible applications for Bose-condensate diagnostics and development of atomic lasers are proposed. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 7, 473–477 (10 October 1996)     

Raman spectroscopy of the components of 18th-century icon painting

The method of Raman spectroscopy is employed in the analysis of lead-containing pigments in ancient Russian painting, transformed pigments, chalk, and drying oil. The Raman spectra of white lead and the mixture of yellow lead oxide, red lead, and lead dioxide are measured, and the test Raman measurements of various fragments of the paint layer of the 18th-century Russian icon Evangelist Mark from the Kirillo-Belozerski State Historical Architectural Art Museum-Reserve are performed. The destructive action of laser radiation on various pigments is evaluated when measuring their Raman spectra.     

Raman analysis of oxide cladded silicon core nanowires grown with solid silicon feed stock

Solid–liquid–solid (SLS) combined with Vapor-liquid–solid (VLS) growth mechanism has been used for synthesizing Core-clad silicon nanowires (SiNWs) by thermal annealing onto two different catalyst substrates (Au/Si and Ni/Ti/Si). It provides a novel method to synthesize SiNWs which is cost-effective, large-area-compatible and may give a higher degree of control of the end product, facilitated by the simple experimental process for further device applications. The first-order Raman peaks of the SiNWs were found to shift and to broaden asymmetrically in comparison to the c-Si Raman peak. Using a phonon confinement model, the average diameter of the wires can be estimated from the Raman spectra but are consistently lower than the diameters measured using high-resolution transmission electron microscopy. We interpret this as due to the confining contribution of the oxide clad. Due to the simplicity of the method, it could be adapted in industry for large scale synthesis of SiNWs with oxide clad for device fabrication, e.g., surround-gate field effect transistors.