Hydrothermally grown nano-manganese oxide on clinoptilolite for low-temperature propane-selective catalytic reduction of NO<Subscript>x</Subscript>

A novel nano-size Mn_xO_y/clinoptilolite catalyst of high activity for propane-SCR reaction of NO_x at low temperatures has been synthesized by a hydrothermal method in a temperature range of 80–180 °C. The optimum synthesis temperature resulting in maximum NO_x conversion was 150 °C. An optimum manganese oxide loading of 0.2 wt.% results in the best catalytic behavior (71% NO_x conversion). All catalysts exhibited an optimal propane-SCR reaction temperature of 200 °C. The optimum catalyst produces no detectable CO (GHSV 27,000 h) at 200 °C. Manganese in the optimum catalyst exists as Mn²⁺ (37.8%), Mn³⁺ (14.2%), and Mn⁴⁺ (48%).

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Graphical abstract Flake-like manganese oxide nanostructures (indicated by an arrow in the TEM picture) next to the clinoptilolite zeolite sheet-like crystals result in a promising low-temperature propane-selective catalytic reduction of NO_x.

     

Study of the third order nonlinear optical properties of Zn<Subscript>1−x</Subscript>Mg<Subscript>x</Subscript>Se and Cd<Subscript>1−x</Subscript>Mg<Subscript>x</Subscript>Se crystals

Third order nonlinear optical susceptibilities χ^<3> of ternary Zn_1−xMg_xSe and Cd_1−xMg_xSe crystals have been measured using standard degenerate four-wave mixing (DFWM) method at 532 nm. The nonlinear transmission technique has been applied to check if our crystals exhibit two-photon absorption. The studied Zn_1−xMg_xSe and Cd_1−xMg_xSe solid solutions were grown from the melt by the modified high-pressure Bridgman method. For both crystals the energy gap increases with increasing Mg content. In the case of Zn_1−xMg_xSe, it was found that the value of third order nonlinear optical susceptibility χ^<3> decreases with increasing Mg content. An explanation of this behaviour results from the dependence of optical nonlinearities on the energy band gap E_g of the studied crystals. In the case of Cd_1txMg_xSe with low content of Mg, no response was observed for the studied wavelength since the energy gap in such crystals is smaller than the photon energy of the used laser radiation. It was also found that the value of third order nonlinear optical susceptibility χ^<3> for Cd_0.70Mg_0.30Se is higher than for Zn_0.67Mg_0.33Se. This behaviour can be understood if one take into consideration that the free carrier concentration in Cd_1−xMg_xSe samples is about four orders of magnitude higher than that in Zn_1txMg_xSe ones with comparable Mg content respectively. It is commonly known that when the electric conductivity increases, the values of nonlinear optical properties increase. From the performed measurements one can conclude that the incorporation of Mg as constituent into ZnSe and CdSe crystals leads to a change of the third order nonlinear optical susceptibilities.     

Anomalous thermal expansion in La<Subscript>2−x</Subscript>Sr<Subscript>x</Subscript>CuO<Subscript>4</Subscript> system

It was found that thermal expansion Δl/l was anomalous in a wide temperature interval for single-and polycrystals of the La_2?xSr_xCuO₄ system with various doping levels: the samples with small Sr content contracted with heating. This effect was observed up to x=0.2. Anisotropy of thermal expansion was revealed, for different crystal directions. The Δl/l anomaly was sensitive, to the oxygen content. These results are consistent with the local bosons model.     

On the interpretation of the phase diagram of La<Subscript>2−x</Subscript>M<Subscript>x</Subscript>CuO<Subscript>4</Subscript>

The difference between the phase diagrams of La_2?x(Ba,Sr)_xCuO₄ and Nd_2?xCe_xCuO₄ is discussed. It is proposed that the discrepancy of x-values corresponding to the transition from antiferromagnetic dielectric state to conducting one (respectively, x≈0.06 in La_2?x(Ba,Sr)_xCuO₄ and x≈0.125 in Nd_2?xCe_xCuO₄) results from non-homogeneous doping of La_2?x(Ba,Sr)_xCuO₄ over the range 0.06<x<0.125, when localized holes are added to each second CuO₂ layer. Therefore the actual phase diagram of the “holedoped” superconductor La_2?x(Ba,Sr)_xCuO₄ coincides with one for the “electron-doped” superconductor Nd_2?xCe_xCuO₄. It is shown that all features observed in La_2?x(Ba,Sr)_xCuO₄ around x=0.125 are clarified on this basis.     

Raman scattering and electrical properties of Tl<Subscript>x</Subscript>Cu<Subscript>1−x</Subscript>GaSe<Subscript>2</Subscript> solid solutions

The results of the study of Raman scattering and photo-emf in Tl _x Cu_1−x GaSe₂ single crystals are presented. The objective of this work was to reveal some features of optical and phonon spectra, to study regularities of their variation with composition and, on this basis, to create prerequisites to extend the possibilities of their practical applications.     

Magnetic phases in Mn<Subscript>1</Subscript>_<Subscript>x</Subscript>Fe<Subscript>x</Subscript>WO<Subscript>4</Subscript> studied by neutron powder diffraction

The magnetic structures of Mn_1-xFe_xWO₄ with x = 0.0, 0.16, 0.21, 0.225, 0.232, 0.24, 0.27, 0.29, and 1.0 were refined from neutron powder diffraction data. The magnetic phase diagram could be completed in the coexistence range of different magnetic structures up to x = 0.29. For the magnetic state at 1.5 K a commensurate antiferromagnetic structure with a propagation vector = (±1/4, 1/2, 1/2) was found for x ⩽ 0.22 while the magnetic spins order with = (1/2, 0, 0) for x ≥ 0.22. In the latter phase, additionally, weak magnetic reflections indexed to an incommensurate ordering with = (- 0.214, 1/2, 0.457) occur in the diffraction pattern up to x = 0.29 indicating the occurence of a reentrant phase. For 0.12 ⩽ x ⩽ 0.29 the low temperature phases are separated from a magnetic high temperature phase showing only magnetic reflections indexed to a spin arrangement with = (1/2, 0, 0). The magnetic phase diagram is discussed qualitatively considering random superexchange between the statistically distributed Mn²⁺- and Fe²⁺-ions in the coexistence range 0.12 ⩽ x ⩽ 0.29 of different magnetic structures related to those of pure MnWO₄ and FeWO₄. Received 9 October 2002 Published online 14 March 2003     

Electrical switching studies on As<Subscript>40</Subscript>Te<Subscript>60-x</Subscript>Se<Subscript>x</Subscript> and As<Subscript>35</Subscript>Te<Subscript>65-x</Subscript>Se<Subscript>x</Subscript> glasses

The I–V characteristics of bulk As₄₀Te_60-xSe_x and As₃₅Te_65-xSe_x glasses have been studied with a current sweep of 0–18 mA-0, over a wide range of compositions (4≤x≤22). All the glasses studied showed a threshold electrical switching behaviour. The number of switching cycles withstood by the samples has been found to depend on the ON-state current. It is seen that the switching voltages increase with increase in selenium content. Further, the switching voltages are found to be almost independent of the thickness of the sample (d), in the range 0.18–0.3 mm. Also, the switching voltages and the number of switching cycles withstood by the samples are found to decrease with temperature. Received: 6 November 2002 / Accepted: 8 November 2002 / Published online: 29 January 2003 RID="*" ID="*"Corresponding author. Fax: +91-80/360-0135, E-mail: sasokan@isu.iisc.ernet.in     

One-dimensional Bi<Subscript>2</Subscript>Mo<Subscript>x</Subscript>W<Subscript>1-x</Subscript>O<Subscript>6</Subscript> sosoloids: controllable synthesis by electrospinning process and enhanced photocatalytic performance

One-dimensional Bi₂Mo_xW_1-xO₆ (x = 0, 0.2, 0.5, 0.67, and 1) photocatalysts have been successfully synthesized for the first time by a straightforward electrospinning technique with a calcination process. The as-formed Bi₂Mo_xW_1-xO₆ nanofibers are composed of inter-linked nanosheets of 30–50 nm in size and characterized by thermogravimetric and differential scanning calorimetric, Fourier transform infrared, Raman spectra, X-ray powder diffraction, scanning electron microscope, Brunauer-Emmett-Teller, transmission electron microscope, UV-Vis spectroscopy, photoluminescence, HPLC, and EIS. The photodegradation behaviors towards organic dyes, including rhodamine B (RhB) and methylene blue (MB) are investigated, and the results illustrate that Bi₂Mo_0.25W_0.75O₆ nanofibers exhibit the highest photocatalytic performance under visible light irradiation than Bi₂Mo_xW_1-xO₆ (x = 0, 0.2, 0.5, 0.67, and 1) samples. The possible mechanisms of the enhanced photocatalytic properties are discussed in detail.     

Electrical properties of a-Ge<Subscript>x</Subscript>Se<Subscript>100-<Emphasis Type="Italic">x</Emphasis></Subscript>

In general, the conductivity in chalcogenide glasses at higher temperatures is dominated by band conduction (DC conduction). But, at lower temperatures, hopping conduction dominates over band conduction. A study at lower temperature can, eventually, provide useful information about the conduction mechanism and the defect states in the material. Therefore, the study of electrical properties of Ge_xSe_100-x in the lower temperature region (room temperature) is interesting. Temperature and frequency dependence of Ge_xSe_{100-x (x} = 15, 20 and 25) have been studied over different range of temperatures and frequencies. An agreement between experimental and theoretical results suggested that the behaviour of germanium selenium system (Ge_xSe_100-x ) have been successfully explained by correlated barrier hopping (CBH) model.     

Thermal characterization of TiC<Subscript>x</Subscript>O<Subscript>y</Subscript> thin films

Thermal wave characterization of thin films used in industrial applications can be a useful tool, not just to get information on the films' thermal properties, but to get information on structural-physical parameters, e.g. crystalline structure and surface roughness, and on the film deposition conditions, since the thermal film properties are directly related to the structural-physical parameters and to the deposition conditions. Different sets of TiC_XO_Y thin films, deposited by reactive magnetron sputtering on steel, have been prepared, changing only one deposition parameter at a time. Here, the effect of the oxygen flow on the thermal film properties is studied. The thermal waves have been measured by modulated IR radiometry, and the phase lag data have been interpreted using an Extremum method by which the thermal coating parameters are directly related to the values and modulation frequencies of the relative extrema of the inverse calibrated thermal wave phases. Structural/morphological characterization has been done using X-ray diffraction (XRD) and atomic force microscopy (AFM). The characterization of the films also includes thickness, hardness, and electric resistivity measurements. The results obtained so far indicate strong correlations between the thermal diffusivity and conductivity, on the one hand, and the oxygen flow on the other hand.     

Preparation and properties of CO<Subscript>x</Subscript> films

New types of amorphous graphite-like CO_x films were obtained by two ways: (i) magnetron sputtering of a graphite target in the gas mixture Ar+O₂; and (ii) air annealing at 250–300 °C of a-C films deposited by magnetron sputtering in Ar. These films contain at most 18–22% atomic oxygen, depending on the way of preparation. They remain stable in air and vacuum up to 300 °C. The transition from graphite-like a-C to a-CO_0.2 is accompanied by a sharp increase in electrical resistivity and IR transmittance. Two characteristic absorption bands at approximately 1700 and 1605 cm^-1 appear and the G band in the Raman spectrum shifts to approximately 1605 cm^-1. Electron diffraction reveals that only those films with 002 interlayer distance increased with respect to that of graphite may be saturated with oxygen up to approximately 22 at.%, until they become strongly vaporized. PACS 61.43.Dq; 78.30.Ly; 81.15.Cd; 81.40.Ef     

Investigation of the temperature coefficient of the forbidden band energy of CdSe<Subscript>1−x</Subscript>S<Subscript>x</Subscript> semiconductor nanostructures

The dependence of the semiconductor forbidden band energy temperature coefficient on the sizes of CdSe_1?xS_x nanocrystals embedded in a silicate glass is investigated experimentally and theoretically. It is revealed that the temperature coefficient dependence on the sizes of nanocrystals has a maximum. This behavior is explained by the reduction of nanocrystalline inclusion sizes at heating, which occurs in view of the more strong expansion of the matrix.     

Magnetic phase diagram of the Bi<Subscript>1-<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript>x</Subscript>MnO<Subscript>3</Subscript> manganites

The magnetic and elastic properties of the Bi_1-xCa_xMnO₃ manganites are studied. The phase transformations revealed are ferromagnet-spin glass (x≥0.15) and spin glass-charge-ordered antiferromagnet (x≥0.25). The ferromagnetic state is characterized by ordering of the Mn³⁺d _x ²-y orbitals. It is suggested that thespin glass state originates from local static Jahn-Teller distortions. The antiferromagnetic charge-ordered and the spin-glass disordered phases coexist in samples with 0.25<x<0.32, which may be due to the charge order-disorder phase transformation being martensitic in character. The magnetic phase diagram is constructed.     

Magnetic Properties of Fe<Subscript>4-y</Subscript>Al<Subscript>y</Subscript>C<Subscript>x</Subscript> Antiperovskite Compound

The crystalline structure, change of magnetization, coercive force and remanent induction of Fe_4-yAl_yC_x antiperovskite were investigated depending on the concentration of alloying elements. Correlation between atomic and magnetic ordering was established. Self-consistent calculations of the electronic structure of Fe_4-yAl_yC_x with hypothetical crystal structures close by the composition to the experimentally studied antiperovskites confirmed the necessity of taking into account non-stoichiometry of this compound. Values of the magnetic moment and the heat of formation for all the structures under investigation were calculated.     

Structure,transport and magnetic properties of the double perovskite (Ca<Subscript>2-2x</Subscript>Sr<Subscript>2x</Subscript>)FeMoO<Subscript>6</Subscript>

In this paper we report the results of a detailed investigation of the double perovskite (Ca_2-2xSr_2x)FeMoO₆ system. Chemical size effects on structural, electrical, and magnetic properties caused by the substitution of isovalent, larger Sr ions into the smaller Ca sites, resulting in (Ca_2-2xSr_2x)FeMoO₆, have been examined. The compounds crystallize in the monoclinic space group P2₁/n for 0.0x<0.2, the orthorhombic space group Pbnm for 0.2x<0.4, and the tetragonal space group I4/m and I4/mmm for x0.4. Examination of the resistivity of all compounds reveals a metallic behavior which is well described by a Tⁿ dependence except for x=1.0. These n values change from 1 to 2 as T decreases lower than T_c. This is indicative of a variation in the transport mechanism at T_c. The ferrimagnetic transition temperature T_c increases with increasing x from 318 (x=0.0) to 393 K (x=1.0). For all samples, the saturation magnetization at 82 K obeys M_s3.5_B/(formula unit), compared to a theoretical spin-only moment of 4_B/(formula unit) for a perfectly ordered compound. PACS 74.25.Fy; 74.25.Ha     

Glass-forming ability and thermal stability of Fe<Subscript>62</Subscript>Nb<Subscript>8−x</Subscript>Zr<Subscript>x</Subscript>B<Subscript>30</Subscript> and Fe<Subscript>72</Subscript>Zr<Subscript>8</Subscript>B<Subscript>20</Subscript> amorphous alloys?

Glass-forming ability (GFA) and thermal stability of Fe₆₂Nb₈B₃₀, Fe₆₂Nb₆Zr₂B₃₀ and Fe₇₂Zr₈B₂₀ at % amorphous alloys were investigated by calorimetric (DSC and DTA) measurements. The crystallization kinetics was studied by DSC in the mode of continuous versus linear heating and it was found that both the glass transition temperature, T _g , and the crystallization peak temperature, T _p , display strong dependence on the heating rate. The partial replacement of Nb by Zr leads to lower T _g and T _x temperatures and causes a decrease of the supercooled liquid region. JMA analysis of isothermal transformation data measured between T _g and T _x suggests that the crystallization of the Fe₆₂Nb₈B₃₀ and Fe₆₂Nb₆Zr₂B₃₀ amorphous alloys take place by three-dimensional growth with constant nucleation rate. Nb enhances the precipitation of the metastable Fe₂₃B₆ phase and stabilizes it up to the third crystallization stage. Zr addition increases the lattice constant of Fe₂₃B₆ and, at the same time, decreases the grain size.     

Electronic structure of paramagnetic In<Subscript>1-x</Subscript>Mn<Subscript>x</Subscript> As nanowires

The electronic structure, spin splitting energies, and g factors of paramagnetic In_1-xMn_xAs nanowires under magnetic and electric fields are investigated theoretically including the sp-d exchange interaction between the carriers and the magnetic ion. We find that the effective g factor changes dramatically with the magnetic field. The spin splitting due to the sp-d exchange interaction counteracts the Zeeman spin splitting. The effective g factor can be tuned to zero by the external magnetic field. There is also spin splitting under an electric field due to the Rashba spin-orbit coupling which is a relativistic effect. The spin-degenerated bands split at nonzero k_z (k_z is the wave vector in the wire direction), and the spin-splitting bands cross at k_z = 0, whose k_z-positive part and negative part are symmetrical. A proper magnetic field makes the k_z-positive part and negative part of the bands asymmetrical, and the bands cross at nonzero k_z. In the absence of magnetic field, the electron Rashba coefficient increases almost linearly with the electric field, while the hole Rashba coefficient increases at first and then decreases as the electric field increases. The hole Rashba coefficient can be tuned to zero by the electric field.     

Piezoelectric spectroscopic studies of Zn<Subscript>1-x-y</Subscript>Be<Subscript>x</Subscript>Mn<Subscript>y</Subscript>mixed crystals

This paper presents results of experimental and theoretical piezoelectric studies of a group of mixed crystals of the type Zn_{1 - x - y}Be_xMn_ySe. The fittings of theoretical to experimental amplitude and phase piezoelectric spectra were performed in a modified Jackson and Amer model. The influence of the surface treatment such as grinding, polishing and etching on the PZE spectra is analysed in the model of surface defects applied for the interpretation of the spectra for energies of photons below the energy gap of the crystal.     

Reluctance of the YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>x</Subscript> oxygen-deficient ceramics

Influence of an external magnetic field on the reluctance of the YBa ₂ Cu ₃ O _x ceramics is investigated. A significant reluctance of the oxygen-deficient ceramics (with critical temperature T_c < 77 K) is established for a sample in the normal state at T < 160 K. It is demonstrated that after ceramics annealing that restores the oxygen content to a nearly optimum value, the magnetic field has essentially no effect on the sample reluctance at temperatures exceeding T_c. To explain the revealed mechanisms, a model involving ferromagnetic clusters effectively decreasing the free carrier density is used. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 4, pp. 68–71, April, 2007.