Synthesis of Layered Perovskite Oxides, ACa2-xLaxNb3-xTix010 (A = K, Rb, Cs), and Characterization of New Solid Acids, HCa2-xLaxNb3-xTixOlo (0 < x d 2), Exhibiting Variable Bronsted Acidity?

Layered perovskite oxides of the formula ACa~,La,Nb3-,Ti,010 (A = K, Rb, Cs and 0 < x d 2) have been prepared. The members adopt the structures of the parent ACazNb3010. Interlayer alkali cations in the niobium-titanium oxide series can be ion-exchanged with Li+, Na+, NH4+, or H+ to give new derivatives. Intercalation of the protonated derivatives with organic bases reveals that the Bronsted acidity of the solid solution series, HC~ ~ , L ~ ,N~ ~ , T ~ ,dOep~eOnd, s on the titanium content. While the x = 1 member (HCaLaNbzTiOlo) is nearly as acidic as the parent HCazNb3010, the x = 2 member (HLazNbTizOlo) is a weak acid hardly intercalating organic bases with pKa - 11.3. The variation of acidity is probably due to an ordering of Nb/Ti atoms in the triple octahedral perovskite slabs, [Ca~,La,Nb~,Ti,0~0], such that protons are attached to NbO6 octahedra in the x = 1 member and to Ti06 octahedra in the x = 2 member.

(Ba3MTiMO9)-Ti-III-O-V (M-III = Fe, Ga, Y, Lu, M-V = Nb, Ta, Sb) perovskite oxides Synthesis, structure and dielectric properties

We describe the synthesis structures and dielectric properties of new perovskite oxides of the formula (Ba3MTiMO9)-Ti-III-O-V for M-III = Fe Ga Y Lu and M-V = Nb Ta Sb While M-V = Nb and Ta oxides adopt disordered/partially ordered 3C perovskite structures where M-III/Ti/M-V metal-oxygen octahedra are corner connected the M-V = Sb oxides show a distinct preference for the 6H structure where Sb-V/Ti-IV metal-oxygen octahedra share a common face forming (Sb Ti)O-9 dimers that are corner-connected to the (MO6)-O-III octahedra The preference of antimony oxides (Sb-V 4d(10)) for the 6H structure which arises from a special Sb-V-O chemical bonding that tends to avoid linear Sb-O-Sb linkages unlike Nb-V/Ta-V d(0) atoms which prefer similar to 180 degrees Nb/Ta-O-Nb/Ta linkages - is consistent with the crystal chemistry of M-V-O oxides in general The dielectric properties reveal a significant difference among Mill members All the oxides with the 3C structure excepting those with Mill = Fe show a normal low loss dielectric behaviour with epsilon = 20-60 in the temperature range 50-400 degrees C the M-III = Fe members with this structure (M-V = Nb Ta) display a relaxor-like ferroelectric behaviour with large E values at frequencies <= 1 MHz (50-500 degrees C) (C) 2010 Elsevier Masson SAS All rights reserved

Synthesis of Cuprates of Perovskite Structure in the Ba-Pb-Cu-O, Ba-Bi-Cu-O, and Ba-Pb-Tl-Cu-O Systems: Possible High Tc Superconductivity in a Perovskite-like Phase in the Ba-Pb-Tl-Cu-O System

Cubic cuprates (a not, vert, similar 18.6 Å) with a BaCuO2-type structure were obtained in the Ba-Pb-Cu-O and Ba-Bi-Cu-O systems by the reaction of the component oxides at a high temperature (1370-1420 K), followed by quenching. By annealing these phases in oxygen at 1070-1120 K, perovskite-like phase (a not, vert, similar 4.3 Å) of the formulae BaPb1-xCuxO3-y and BaBi1-xCuxO3-y (0 < x ? 0.5) were obtained. A perovskite of nominal composition BaPb0.25Tl0.25 Cu0.5O3-y, prepared by a similar procedure, was found to be superconducting with a Tc of not, vert, similar 70 K.

AM(1-x)Al(x)O(3-x) (A=Na or K; M=Nb or Ta): New anion-deficient Perovskite oxides exhibiting oxide ion conduction

Anion-deficient perovskite oxides of the formula AM(1-x)Al(x)O(3-x) (A = Na or K; M = Nb or Ta) have been prepared for 0 < x less than or equal to 0.5. Diffraction experiments reveal that while the potassium compounds adopt orthorhombic/cubic perovskite structures similar to the parent KNbO3/KTaO3, the sodium compound, NaNb0.5Al0.5O2.5, possesses a brownmillerite/LaSr-CuAlO5-like superstructure. Al-27 NMR spectra show an exclusive tetrahedral oxygen coordination for AI(III) in Na-Nb0.5Al0.5O2.5 (I) and both tetrahedral and octahedral coordination for Al(III) in KNb0.5Al0.5O2.5 (II). The results suggest a long-range and short-range ordering of oxide ion vacancies in I and II respectively. Electrical conductivity measurements show a significant oxide ion conduction for KNb1-xAlxO3-x, with the conductivity increasing with x up to x = 0.5. The differences in the Arrhenius plots of the ionic conductivity of I and II have been rationalized in terms of the long-range and short-range ordering of oxide ion vacancies in the anion-deficient perovskite oxides.

Normal state tunneling conductance of perovskite oxides: Implications for high-Tc superconductors

We have investigated tunneling conductances in disordered, normally conducting perovskite oxides close to the metal�insulator transition. We show that the normal state tunneling conductance of perovskite oxides can be cast in a general form G(V) = G0[1 + curly logical orV/V*curly logical orn] with 1?n?0.5 and where V* is an intrinsic energy scale. The exponent n graduall y increases from 0.5 to 1 as the metal-insulator (M-I) transition is approached. In the high-Tc Bi(2212) cuprates, the normally observed, linear G(V)(n=1) can be made sub-linear (n<1) by substitution of Ca with Y. From the similarity of the linear conductances, we suggest proximity to the M-I transition as a likely cause for this G(V)logical or, bar below V dependence. In systems showing linear conductances (nreverse similar, equals1), we find that ?G/?Vreverse similar, equalsG?0 with ?reverse similar, equals 1 and the intrinsic energy scale V*reverse similar, equals25�75 meV in the different oxides investigated.

Photocatalysis on Fine Powders of Perovskite Oxides

Fine powders of semiconductor oxides have been widely used as photocatalysts for many reactions. Among the various photocatalytic reactions, water splitting has been given much importance, since it is a promising chemical route for solar energy conversion. Perovskite oxides, in particular SrTiO, have been commonly used as photocatalysts because some of them can decompose H,O into H, and 0, without an external bias potential (1). In turn, this is because the conduction band (CB) edges of some of the perovskite oxides are more negative than the H+/H, energy level. Since the catalytic activity is related to the surface properties of the solids, fine powders rather than single crystals are used. Photocatalysis on fine powers can be conveniently discussed in three parts, viz. preparation, characterization and their catalytic activity. Presently, photo-decomposition of water using SrTiO, fine powders is discussed in greater detail, although other photocatalytic reactions on various perovskite oxides are also briefly dealt with.

New uniform solid catalyst for the low-temperature oxidation of carbon monoxide: A triple-layered rare earth perovskite containing Co and Cu ions

Oxygen reactivity and catalytic activity of the cobalt-containing layered defect perovskites, YBa2Cu2CoO7+delta and LaBa2Cu2CoO7+delta, in comparison with LaBa2Cu3O7-delta have been investigated employing temperature-programmed desorption (TPD) and temperature-programmed surface reactions (TPSR) in the stoichiometric and catalytic mode using carbon monoxide as a probe molecule. TPD studies showed evidence for the presence of two distinct labile oxygen species, one at (0 0 1/2) sites and the other at (0 1/2 0) sites in LaBa2Cu2CoO7+delta against a single labile species at (0 1/2 0) in the case of two other oxides. The activation energies for the catalytic oxidation of carbon monoxide by oxygen over LaBa2Cu3O7-delta, YBa2Cu2CoO7+delta, and LaBa2Cu2CoO7+delta have been estimated to be 24.2, 15.9, and 13.6 kcal/mol, respectively. The reactivity and catalytic activity of the oxide systems have been interpreted in terms of the structural changes brought about by substituents, guided by a directing effect of the larger rare earth cation. TPSR profiles, structural analysis, and infrared spectroscopic investigations suggest that the oxygen present at (0 0 1/2) sites in the case of LaBa2Cu2CoO7+delta is accessible to catalytic oxidation of CO through a Mars-Van Krevelen pathway. Catalytic conversion of CO to CO2 over LaBa2Cu2CoO7+delta occurs at 200 degrees C. The enhanced reactivity is explained in terms of changes brought about in the coordination polyhedra around transition metals, enhanced basal plane oxygen diffusivity, and redox potentials of the different transition metal cations.

Quantum corrections to the conductivity in a perovskite oxide: A low-temperature study of LaNi1-xCoxO3 (0?x?0.75)

In this paper we propose to study the evolution of the quantum corrections to the conductivity in an oxide system as we approach the metal-insulator (M-I) transition from the metallic side. We report here the measurement of the low-temperature (0.1 Kperovskite-structure oxide system LaNi1-x CoxO3 (0?x?0.75). LaNiO3 is a metal and LaCoO3 is an insulator. The system is metallic for x?0.65. For all x, at low temperatures, the conductivity (?) rises with temperature (T). Below 2 K, ? follows a power-law behavior, ?(T)=?(0)+?Tm. For samples in the metallic regime, away from the metal-insulator transition (x?0.4), m?0.3�0.4. As the transition is approached [i.e., ?(0)?0], m increases rapidly; and at the transition [?(0)=0, xc?0.65], m?1. On the insulating side (x>0.65), m takes on large values and ?(0)=0. We explain the temperature dependence of ?(T), for T<2 K, on the metallic side (x?0.4), as arising predominantly from electron-electron interactions, taking into account the diffusion-channel contribution (which gives m=0.5) as well as the Cooper-channel contribution. In this regime, the correction to conductivity, ??(T), is a small fraction of ?(T). However, as the M-I transition is approached (x?xc), ??(T) starts to dominate ?(T) and the above theories fail to explain the observed ?(T).

ChemInform Abstract: Slicing the Perovskite Structure into Layers: Synthesis of Novel Three- Dimensional and Layered Perovskite Oxides, ALaSrNb2M(II)O9 (A: Na, Cs)

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Metal-insulator transition in perovskite oxides: Tunneling experiments

In this paper we have investigated the composition-driven metal-insulator (MI) transitions in two ABO3 classes of perovskite oxides (LaNixCo1-xO3 and NaxTayW1-yO3) in the composition range close to the critical region by using the tunneling technique. Two types of junctions (point-contact and planar) have been used for the investigation covering the temperature range 0.4 K

Synthesis and structural characterization of perovskite 0.65Pb(Mg1/3Nb2/3)O-3-0.35PbTiO(3) nanotubes

We report the synthesis and structural characterization of 0.65Pb(Mg1/3Nb2/3)O-3-0.35PbTiO(3) (PMN-PT) nanotubes prepared by a novel sal-gel template method. X-ray diffraction (XRD) and selected-area electron diffraction (SAED) investigations demonstrated that the postannealed (650 degrees C for 1 h) PMN-PT nanotubes were polycrystalline with perovskite crystal structure. The field emission scanning electron microscope (FE-SEM) shows that as prepared PMN-PT nanotubes were hollow with diameter to be about 200 nm. High resolution transmission electron microscope (HRTEM) analysis confirmed that the obtained PMN-PT nanotubes made up of nanoparticles (10-20 nm) which were randomly aligned in the nanotubes. Energy-dispersive X-ray spectroscopy (EDX) analysis confirmed the stoichiometric 0.65Pb(Mg1/3Nb2/3)O-3-0.35PbTiO(3). The possible formation mechanism of PMN-PT nanotubes was proposed at the end. (C) 2011 Elsevier B.V. All rights reserved.

A[Bi3Ti4O13] and A[Bi3PbTi5O16] (A = K, Cs): New n=4 and n=5 members of the layered perovskite series, A[A ' n-1B nO3n+1], and their hydrates

We describe the synthesis and structural characterization of new layered bismuth titanates, A[Bi3Ti4O13] and A[Bi3PbTi5O16]for A = K, Cs, corresponding to n = 4 and 5 members of the Dion-Jacobson series of layered perovskites of the general formula, A[A'n-1BnO3n+1]. These materials have been prepared by solid state reaction of the constituents containing excess alkali, which is required to suppress the formation of competitive Aurivillius phases. Unlike the isostructural niobates and niobium titanates of the same series, the new phases reported here are spontaneously hydrated-a feature which could make them potentially useful as photocatalysts for water splitting reaction. On hydration of the potassium compounds, the c axis expands by ca. 2 Angstrom and loses its doubling [for example, the tetragonal lattice parameters of K[Bi3Ti4O13] and its dihydrate are respectively a = 3900(1)Angstrom c 37.57(2) Angstrom; a 3.885(1) Angstrom, c = 20.82(4) Angstrom]; surprisingly, the cesium analogues do not show a similar change on hydration.

Investigation of valence states in the perovskite oxides, LaAFeNbO(6) (A = Ca, Sr)

Compounds of the type, LaAFeNbO(6) (A = Ca Sr) have been synthesized to study the electrical and magnetic properties and to examine valence degeneracy. The results show that valence degeneracy is not operative and the compounds are insulating. Magnetic susceptibility data show that part of the Fe is in Fs(2+) state, thus oxidizing part of Nb4+ to Nb5+ by an internal redox mechanism. The presence of mixed valent Fe is confirmed by Mossbauer spectra. (C) 1999 Elsevier Science B.V. All rights reserved.

LiSr1.65 square 0.35B1.3B ' O-1.7(9) (B = Ti, Zr; B ' = Nb, Ta): New lithium ion conductors based on the perovskite structure

We describe the design and synthesis of new lithium ion conductors with the formula, LiSr(1.65)rectangle(0.35)B(1.3)B'O-1.7(9) (rectangle = vacancy; B = Ti, Zr; B' = Nb, Ta), on the basis of a systematic consideration of the composition-structure-property correlations in the well-known lithium-ion conductor, La-(2/3-x)Li(3x)rectangle((1/3)-2x)TiO3 (I), as well as the perovskite oxides in Li-A-B,B'-O (A = Ca, Sr, Ba; B = Ti, Zr; B' = Nb, Ta) systems. A high lithium-ion conductivity of ca. 0.12 S/cm at 360 degrees C is exhibited by LiSr(1.65)rectangle(0.35)Ti(1.3)Ta(1.7)O(9) (III) and LiSr(1.65)rectangle(0.35)Zr(1.3)Ta(1.7)O(9) (IV), of which the latter containing stable Zr(IV) and Ta(V) oxidation states is likely to be a candidate electrolyte material for all-solid-state lithium battery application. More importantly, we believe the approach described here could be extended to synthesize newer, possibly better, lithium ion conductors.