Effect of strontium substitution on the activity of La2-xSrxNiO4 (x=0.0-1.2) in NO decomposition

The aim of this work is to study the effect of Sr substitution on the redox properties and catalytic activity of La2-xSrxNiO4 (x = 0.0-1.2) for NO decomposition. Results suggest that the x = 0.6 sample shows the highest activity. The characterization (TPD, TPR, etc.) of samples indicates that the x = 0.6 sample possesses suitable abilities in both oxidation and reduction, which facilitates the proceeding of oxygen desorption and NO adsorption. At temperature below 700 degrees C, the oxygen desorption is difficult, and is the rate-determining step of NO decomposition. With the increase of reaction temperature (T > 700 degrees C), the oxygen desorption is favorable and, the active adsorption of NO on the active site (NO + V-o + Ni2+ -> NO--Ni3+) turns out to be the rate-determining step. The existence of oxygen vacancy is the prerequisite condition for NO decomposition, but its quantity does not relate much to the activity.

Active site structure of NO decomposition on perovskite(-like) oxides: An investigation from experiment and density functional theory

Active site structure for NO decomposition carried out on perovskite-like oxides were discussed based on the N-2 yield measured from LaSrNi1-x,AlxO4 with different B-site cations and from La2-ySryCuO4 with different crystal phases. Results show that the active site contains two oxygen vacancies, two transition metals, and one lattice-oxygen, with the oxygen vacancy locating on the apex of MO6 octahedron, and the lattice oxygen locating between the two transition metals (i.e., M-O-M plane). Density functional theory (DFT) analysis to the structure shows that this new active site is the most active structure for NO adsorbing, and hence, for NO decomposition. The similar trend of the relative energies that are required for the formation of oxygen vacancies with f form (calculated from DFT), the amount of oxygen vacancies, and the activities (N-2 yield) certifies this result further.

Structural and magnetic properties of Sr2Fe1−xGaxMoO6 (0≤x≤0.25)

We have investigated the structure, magnetization and magnetoresistance (MR) of the double perovskite compounds Sr2Fe1−xGaxMoO6 (0≤x≤0.25). Rietveld refinement results show that the anti-site defects (ASDs) concentration increases with x, giving rise to highly disordered samples at the B/B positions, for the highest doping levels. The evolution of bond lengths and ions oxidation states could be understood by the distribution of trivalent Ga ions at the B/B positions, which leads to the formation of more disorder structure. The saturation magnetization and Curie temperature decreased with the Ga content increases in the samples, and their origin was found that the cations disorder for the Ga-doped compounds is annihilating double exchange mechanism due to the presence of significant amounts of Fe and Ga cations on the B site. The low-field magnetoresistance of Sr2FeMoO6 (SFMO) can be greatly enhanced by replacing the Fe by the nonmagnetic Ga ion up to a temperature of 300 K,since Ga ions may act as a barrier for electron transport along the chain in the ferromagnetic segregation and weaken the ferromagnetic exchange.

Simultaneous determination of dopamine and ascorbic acid at an in-site functionalized self-assembled monolayer on gold electrode

The in-site functionalization of 4-aminothiophenol (4-ATP) self-assembled monolayer on gold electrode at physiological pH yields a redox active monolayer of 4'-mercapto-N-phenylquinone diimine (MNPD). The functionalized electrode exhibits excellent electrocatalytic responses towards dopamine (DA) and ascorbic acid (AA), reducing the overpotentials by about 0.22 V and 0.34 V, respectively, with greatly enhanced current responses. Due to its different catalytic activities toward DA and AA, the modified electrode resolves the overlapping voltammetric responses of DA and AA into two well-defined voltammetric peaks by differential pulse voltammetry (DPV), which can be used for the simultaneous determination of these species in a mixture. The catalytic peak current obtained from DPV was linearly related to DA and AA concentration in the ranges of 5.0 x 10-6 - 1.25 x 10-4 M and 8.0 x 10-6 - 1.3 x 10-4 M with correlation coefficient of 0.999 and 0.998, respectively. The detective limits (3sigma) for DA and AA were found to be 1.2 x 10-6 M and 2.4 x 10-6 M, respectively.

An investigation of low-field magnetoresistance in the double perovskites Sr2Fe1-xZnxMoO6, x=0, 0.05, 0.15 and 0.25

The electrical, magnetic and transport properties of Zn doped polycrystalline samples of Sr2Fe1-xZnxMoO6 ( x = 0, 0.05, 0.15 and 0.25) with the double perovskite structure have been investigated. The subtle replacement of Fe3+ ions by Zn2+ ions facilitates the formation of a more ordered structure, while further substitution leads to disordered structure because of the presence of a striped phase. Analysis of the x-ray powder diffraction patterns based on Rietveld analysis indicates that the replacement of Fe3+ by Zn2+ ions favours the formation of Mo6+ ions. The spin-glass behaviour can be explained on the basis of the competition between the antiferromagnetic superexchange and the ferromagnetic double-exchange interaction. The low-field magnetoresistance was moderately enhanced at x = 0.05, and its origin was found to be the competition between the decrease of the concentration of the itinerant electrons and the weaker antiferromagnetic superexchange in the antiphase boundaries. An almost linear negative magnetoresistance in moderate field has been observed for x = 0.25. A possible double-exchange mechanism is proposed for elucidating the observations; it also suggests a coexistence of (Fe3+, Mo5+) and (Zn2+, Mo6+) valence pairs.

Effect of Ce and MgO on NO decomposition over La1-x-Ce-x-Sr-Ni-O/MgO

Ce and MgO were added simultaneously to La-Sr-Ni-O catalyst and a substantial enhancement of activity for NO decomposition was observed, which may be attributed to the formation of a new highly active site caused by the addition of Ce and MgO.

Hydrothermal synthesis, structure, and characterization of two one-dimensional chainlike hybrid complexes [(CuX)(2)(o-phen)](infinity) (X = Br, Cl; o-phen = o-phenanthroline)

Two novel organic-inorganic hybrid complexes [(CuX)(2)(o-phen)](infinity) (X = Br (1), Cl (2); o-phen = o-phenanthroline) have been synthesized hydrothermally and characterized structurally by elemental analyses, IR, ESR, XPS spectrum, TG analyses and single-crystal X-ray diffraction. Both title compounds exhibit novel one-dimensional chainlike copper halide scaffolding constructed by the unusual [Cu3X3] hexagon motifs by sharing opposite edges, where a single Cu site of each [Cu3X3] hexagon is chelated with N donors of o-phen group. To our knowledge, such basic o-phen-copper halide skeleton has not been reported hitherto. Moreover, TG analyses indicate that both title compounds possess high thermal stability.

Study on highly ordered luminescent Langmuir-Blodgett films of heteropolytung state complexes containing lanthanide

Luminescent thin films of heteropolytungstate complexes containing lanthanide (europium or samarium) were successfully fabricated by the Langmuir-Blodgett (LB) technique. The pressure-area isotherm of the monolayer of dimethyldioctadecylammonium. bromide (DODA) is modified rather markedly when the subphase contains the complex of Na9EuW10O36 or Na9SmW10O36. The above results indicate that the monolayer of DODA has a strong interaction with the polyanions of EuW10O369-. (or SmW10O369-). X-ray photoelectron spectra and fluorescent spectra verify that europium and tungsten atoms are 36 36 incorporated into the LB films. Ultraviolet (UV), fluorescent spectra and low-angle X-ray diffraction experiments demonstrate that these LB films have a well-defined lamellar structure. The LB film containing EuW10O369- can give off strong fluorescence 16 on UV irradiation. The characteristic emission behaviors of europium ions in LB films and in the powder of Na9EuW10O369- are discussed. It is found that the intensity ratio of the D-5(0)-F-7(2) transition to the D-5(0)-->F-7(1) transition in LB film is quite different from that in the powder of Na9EuW10O36. The difference of the ratio indicates that the site symmetry of europiurn is distorted in LB film, which is probably due to the strong electrostatic interactions between DODA and polyanions.

The site symmetry of Eu3+ in ZnS : Eu nanoparticle

Nanosized ZnS doped with different concentrations of Eu3+ were prepared and analyzed by x-ray diffraction technique. The experimental results show that ZnS belongs to the cubic structure. From the photoluminescence (PL) emission spectra, it can be seen that the ratio of the emission intensity of Eu3+ 616 nm to that at 590 nm increases as the increasing of Eu3+. This phenomenon reveals that the site symmetry of Eu3+ reduces as the increasing of Eu3+.

Investigation of Pr valence and relationship between bond covalency and T-c in Y1-xPrxBa2Cu3O7 (x = 0-1)

The valence of Pr and relationship between bond covalency and T-c in Y1-xPrxBa2Cu3O7 (x = 0-1) have been studied using complex chemical bond theory. The results indicate that the depression of superconductivity in Y1-xPrxBa2Cu3O7 can be reasonably explained by bond covalency difference for the bonds between CuO2 plane and CuO chain. T-c decreases with the decreasing of bond covalency difference and reaches zero when bond covalency difference is zero (or bond covalency in CuO2 exceeds that in CuO chain) at Pr concentration 0.55 and valence +3.30. These are in good agreement with the experiments and meanwhile suggest that the valence of Pr is + 3.30 in Y1-xPrxBa2Cu3O7. The results also indicate that for Pr valence less than +3.15, superconductivity always exists for whatever Pr concentration, whereas for Pr with a valence of +4.0, superconductivity disappears as soon as Pr concentration exceeds 0.19. This supports with the viewpoint that higher valence Pr will contribute more electrons to CuO2 plane, filling the mobile holes responsible for conduction. For PrBa2Cu3O7 with no Ba-site Pr, our calculation suggests that it will be a superconductor if the average valence of Pr is less than +3.15. (C) 1998 Published by Elsevier Science B.V. All rights reserved.

Mossbauer spectra of Fe-57 in a thick film of YBa2(Cu0.97Fe0.03)(3)O7-x irradiated by a large dose of gamma-rays

Mossbauer spectra of Fe-57 in a thick film YBa2(Cu0.97Fe0.03)(3)O7-x irradiated by a large dose of gamma-rays from Co-60 have been measured. The variation of the relative intensities of some subspectra of Fe-57 in the. Mossbauer spectra of the thick film YBa2(Cu0.97Fe0.03)(3)O7-x after irradiation can be observed. This variation indicates that the change of the coordination environment around some Fe atoms in the lattice occurs due to irradiation. The relative intensity of subspectrum D1(Fe) at the Cu(1) site decreases and that of subspectrum D4(Fe) at the Cu(1) site increases. This may be because of the possible oxygen atom hopping between the coordination environments of D1(Fe) and D4(Fe) in the lattice caused by irradiation. The effect of irradiation on the coordination environment around the Fe atom at the Cu(2) site is not appreciable. (C) 1997 Elsevier Science B.V.

Characterization and catalytic behavior of La2-x(Sr,Th)(x)CuO4+/-lambda in reaction NO+CO

Two mixed oxide systems La2-xSrxCuO4+/-lambda(0.0 less than or equal to x less than or equal to 1.0) and La2+xThxCuO4+/-lambda(0.0 less than or equal to x less than or equal to 0.4) with K2NiF4 structure were prepared by varying re values; Their crystal structures were studied by means of XRD and IR spectra. The average valence of Cu ion at B site, nonstoichiometric oxygen (A) and the chemical composition in the bulk and on the surface of the catalysts were measured by means of chemical analysis and XPS. The catalytic behavior in reaction CO + NO was investigated under the regular change of average valence of Cu ion at B site and nonstoichiometric oxygen (lambda). Meanwhile, the adsorption and activation of the small molecules NO and the mixture of NO + CO over the mixed oxide catalysts were studied by means of MS-TPD. The catalytic mechanism of reaction NO + CO over these oxide catalysts were proposed; and it has been found that, at lower temperatures the activation of NO is the rate determining step and the catalytic activity is related to the lower valent metallic ion and its concentration, while at higher temperatures the adsorption of NO is the rate determining step and the catalytic activity is related to the oxygen vacancy and its concentration.

X-Ray Photoelectron Spectroscopy Study of LaMn1-xFexO3 (x=0-1) Oxides

The redox potential, surface composition and oxygen species of a series of complex oxides LaMn1-xFexO3 (x=0-1) having perovskite structure (ABO(3)) have been investigated by means of XI'S. The variation of binding energies referring to Mn2p and Fe 2p under different treatment offerred an obvious evidence of redox between Mn and Fe, which could be expressed as Mn4+ + Fe(3-delta)+ Mn(4-delta)+ Fe3+ Feat Through computer fit three kinds of adsorbed oxygen species (O-I, O-II, O-III) have been evaluated based on the XPS spectra of O1s. From the variation of contents of different oxygen species, it could be concluded that. the redox occuring in the surface might be related with the adsorbed oxygen species O-I and O-II, furthermore the possibility of transfer of electron between adsorption site and oxygen was also discussed.