Catalysis of the rare earth containing mixed oxides Ln(2)CuO(4) in phenol hydroxylation

Mixed oxides Ln(2)CuO(4+/-lambda)(Ln = La, Pr, Nd, Sm, Gd) with K2NiF4 structure were prepared. Their crystal structures were studied with XRD and IR spectra. Meanwhile, the average valence of Cu ions and nonstoichiometric oxygen (lambda) were determined through chemical analyses. Catalysis of the above-mentioned mixed oxides in the phenol hydroxylation was investigated. Results show that the catalysis of these mixed oxides has close relation with their structures and composition. Substitution of A site atom in Ln(2)CuO(4+/-lambda) has a great influence on their catalysis in the phenol hydroxylation.

Preparation, physico-chemical behavior and catalytic property for ammonia oxidation of perovskite like mixed oxides La2-xSrxCuO4-lambda

A series of Sr2+ doped perovskite like oxides La2-xSrxCuO4-lambda (x = 0 similar to 1) were prepared, the structure, lattice parameters, content of Cu3+, oxygen vacancies created by Sr2+ substitution and composition of these complex oxides were studied by XRD and iodic titration method. The redox ability,active oxygen species and surface image were evaluated and analyzed with TPD, TG, XPS and SEM measurements. The catalytic activity for ammonia oxidation over these oxides was tested, and the relationship among the catalytic properties, structure, nonstoichiometric oxygen,redox ability and surface behavior were correlated and some information on the mechanism of ammonia oxidation was obtained.

Influences of acid treatments of active carbons on no reduction over carbon-supported copper oxides

Active carbon supported copper oxides were used in NO reduction. The conversions of NO reduction depends strongly on surface oxygen-containing groups on the active carbons, among them the carboxyls and lactones favored remarkably the NO reduction. However, hydrochloric acid treatment led to the decomposition of the carboxyls and lactones on C2 and C3, decreasing their reactivities for NO reduction. Concentrated HNO3 treatment of active carbon produced higher conversions of NO reduction at relatively low temperatures due to the marked increase in the amounts of the carboxyls and lactones.

Y-Ba-Cu-O mixed oxides for production of diphenols in liquid-solid phase

Superconductor mixed oxides were often used as catalysts at higher temperature in gas phase oxidations, and considered not suitable for lower temperature reactions in the liquid-solid phase; here the catalysis of YBa2Cu3O7+/-x and Y2BaCuO5+/-x in the phenol hydroxylation at lower temperature with H2O2 as oxygen donor was studied, and found that the superconductor YBa2Cu3O7+/-x, has no catalytic activity for phenol hydroxylation, but Y2BaCuO5+/-x does, even has better catalytic activity and stability than most previously reported ones. With the studies of catalysis of other simple metal oxides and perovskite-like mixed oxides, a radical substitution mechanism is proposed and the experimental facts are explained clearly, and draw a conclusion that the perovskite-like mixed oxides with (AO)(ABO(3)) and (AO)2(ABO(3)) structure have better catalytic activity than the simple perovskite oxides with (ABO(3))(3) structure alone, and (AO) structure unit is the key for the mixed oxides to have the phenol hydroxylation activity. No pollution of this process is very important for its further industrial application.

Electrochemical preparation of microelectrodes modified with non-stoichiometric mixed-valent molybdenum oxides

A compact non-stoichiometric molybdenum (VI, V) oxide of blue film was grown on carbon fiber (CF) microelectrode surface be cycling the potential between + 0.2V and - 0.70V in a freshly prepared Na2MoO4 solution containing 5 x 10(-3) mol/L H2SO4. The quantity-of the oxide is controlled by the charge passing the electrode. The electrochemical pretreatment of CF microelectrode not only mises the deposition velocity of molybdenum oxide on CF surface, but also improves greatly the cyclic voltammetric behavior of the molybdenum oxide film prior to the electrodeposition. The cathodic processes are believed to yield the hydrogen molybdenum oxide bronzes HxMoO3(0 < x < 2), or substoichiometric lower molybdenum oxides with the formula MoO3-y(0 < y < 1). The anodic response results from the reversible oxidation of molybdenum bronze/Mo(V) centers [or perhaps Mo(IV) in more reduced coatings], to Mo(VI). Further information was gained about the chemical composition and valent state of Mo from XPS and SEM.

Superconductor mixed oxides La2-xSrxCuO4+/-lambda for catalytic hydroxylation of phenol in the liquid-solid phase

Superconductor mixed oxides are often used as catalysts at high temperature in gas-solid phase oxidations and considered not suitable for lower temperature reactions in the liquid-solid phase; here the catalysis of La2-xSrxCuO4+/-lambda (x = 0, 0.1, 0.7, 1) mixed oxides in phenol hydroxylation at lower temperatures are studied, and we find that the value of x has a significant effect on catalytic activity: the lower its value, the higher the catalytic activity; a mechanism is proposed to explain the experimental phenomena.

Crystal structure of polypropylene filled with rare earth oxides

The effect of a fine powder of Y2O3, Nd2O3, and Ho2O3 on the crystal structure of isotactic polypropylene (iPP) was studied with WAXD and DSC techniques. The results showed that the addition of the three rare earth oxides (REOs) can increase the crystallite size of the alpha-form crystal and the degree of crystallinity of iPP at an annealing temperature of 120 degrees C and that both Y2O3 and Nd2O3 are the beta-nucleator of iPP. REOs enhance the overall growth rate of the spherulites of iPP. All the iPP samples filled with REOs which were crystallized isothermally at 132 degrees C from the melt exhibited their melting peaks of the beta-form on the DSC heating traces, indicating that the REOs are the nucleating agents for both the alpha- and beta-forms of iPP under isothermal conditions. (C) 1996 John Wiley & Sons, Inc.

Relationship between the structure and catalytic activity of La2-xSrxNiO4-lambda(0<=x<=1) mixed oxides for NH3 oxidation

A series of samples having the composition of La2-xSrxNiO4(0 less than or equal to x less than or equal to 1) were prepared and used as catalysts for NH3 oxidation. It was found that the La and oxygen vacancies exist in the La2-xSrxNiO4-lambda(0 less than or equal to x less than or equal to 1). The unit cell volume decreases with the increase of x. For bath c and a parameters there appeared a turning point at x = 0.5. Doping with a lower valence cation Sr2+ in the case of La2NiO4 resulted in an increase of Ni3+, consequently the formation of oxygen vacancies, the increase of reducing ability and the increase of catalytic activity. In the oxygen TPD of La2-xSrxNiO4(0 less than or equal to x less than or equal to 1) appeared three peaks, the alpha' peak at about 400K was attributed to the surplus oxygen desorption, the a peak at 700K which approaches to a maxium at x = 0.6 was attributed to the oxygen adsorbed at oxygen vacancies. The beta peak at about 1000K which depends closely on the x and favors the catalytic activity was attributed to the reduction of Ni3+. The catalytic activity of La-2-x SrxNiO4 mixed oxides in the NH3 oxidation in general could be attributed to the extent of the redox reaction: 2Ni(2+) + O-2 + V-0(..) reversible arrow 2Ni(3+) + 20(-) where V-0(..) representes the oxygen vacancies and O- the oxygen species adsorbed at the vacancies.

Investigation of Catalysis of Y-Ba-Cu-O Mixed Oxides in Phenol Hydroxylation

Superconductor Y-Ba-Cu-O mixed oxides were synthesized and their catalysis in phenol hydroxylation was studied too. Results show that, Y2BaCuO5 has better activity than that of YBa2Cu3O7-x, With the catalysis study of another mixed oxide La2CuO4 a conclusion that AO structure unit is the key for mixed oxides to have high activity in phyenol hydroxylation was drawn. Meanwhile, the effects of reaction temperature, medium and medium (water) pH on phenol hydroxylation catalyzed by Y2BaCuO5 and the stability of the mixed oxides were also studied.

PREPARATION STRUCTURE AND PHYSICAL-PROPERTIES OF NEW SILVER LANTHANIDE MOLYBDENUM OXIDES [AGLNMO(2)O(8)(LN=LA-ND AND SM)]

We present the synthesis of AgLnMo(2)O(8) compounds with Ln = La-Nd and Sm. These compounds represent a scheelite-type structure characterized by MoO4- tetrahedrons. IR spectra show five absorption peaks in the region of 1000-400cm(-1), around 800cm(-1) and 400cm(-1), which correspond to the modes of the tetrahedral MoO42- groups. All of AgLnMo(2)O(8) (Ln = La-Nd and Sm) oxides are dielectric materials at room temperature. The temperature dependence of the magnetic susceptibility ofAgLnMo(2)O(8) (Ln = Ce-Nd and Sm) shows Curie-Weiss law behavior from 100K to 300K. This indicates that both Ce and Pr exist in +3 oxidation state in AgLnMo(2)O(8). For AgLaMo2O8, diamagnetic properties are found as expected.

SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF THE DAWSON-TYPE TUNGSTOPHOSPHATE HETEROPOLY COMPLEXES SUBSTITUTED BY NIOBIUM

Eight new complexes alpha(2)-M(7-m)H(m)[P2W17NbO62]. H2O and alpha-1, 2, 3-M(g-m)H(m) [P2W15Nb3O62]. XH(2)O(M=K, TMA, TEA, TBA) were synthesized and characterized by IR and UV spectroscopy, polarography, XPS and XRD methods. P-31 and W-183 NMR studies show that the niobium atoms in the anions are on the polar sites. The crystal of alpha-1, 2, 3-K7H2 [P2W15Nb3O62]. 30H(2)O is hexagonal, its cell parameters: a=1.9836(4), b=1.9836(9), c=1.5498(6)nm, alpha=beta=90 degrees, gamma=120 degrees.

STUDIES ON SYNTHESIS, CHARACTERIZATION AND CATALYTIC PROPERTIES OF LAN+1NINO3N+1 MIXED OXIDES

A series of (AO) (ABO(3))(n)(A = La, B = Ni, n = 1 similar to 4) type mixed oxides were synthesized and characterized by means of XRD, XPS, IR, TPD, TPR. Their structure characteristics and redox properties were studied. The nonstoichiometry (lambda) of oxygen and the valence of transition metal Ni were determined by using chemical analysis method. The catalytic activities of this series of mixed oxides for complete oxidation of CO and CH4 were examined and the relationships among activity, composition and structure were discussed.

CHARACTERIZATION OF OXIDES AND HALOGENIDES OF CERIUM BY ESCA .2. AUGER PEAKS OF CE-M5N45N45

The larger chemical shift of cerium compounds was discoveried. The chemical states of the cerium compounds were identified by the chemical shifts of Auger energy. The changes in Anger energy and parameters are principally due to the changes in extra-atomic relaxation or polarization energy. The increase of the polarizable properties in anions of cerium compounds corresponds to the increase of Auger energy and parameter. The Auger parameter can be measured more accurately. Ce(CF3COO)(x)Cl-3-x was also studied by ESCA. It is shown that the electron density at cerium atom increases with the increase of x, while the electron density at oxygen atom decreases.

STUDIES ON THE SYNTHETIC, STRUCTURAL, ELECTRICAL, AND MAGNETIC-PROPERTIES OF THE NEW LAYERED OXIDES LN(2)MCO(2)O(7) (LN=SM, GD, M=SR, BA)

Three new oxides Ln(2)MCo(2)O(7) (Ln = Sm, Gd; M = Sr, Ba) have been synthesized in solid state reaction method. The powder X-ray diffraction spectra show that they are all isostructural with Sr3Ti2O7. The electrical resistivities in the temperature range 300-1100 K show that they are all semiconductors, and a transition to metals is observed at 1053, 1053, and 573 K for Sm2SrCo2O7, Gd2SrCo2O7, and Sm2BaCo2O7, respectively. The magnetic suspectivities of Gd2SrCo2O7 in the temperature range 300-673 K fit the Curie-Weiss law well. A plateau is observed in the curves of Sm(2)MCo(2)O(7) (M = Sr, Ba) which is attributed to the configuration state change of Co(III) from low spin to high spin. (C) 1995 Academic Press, Inc.

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.