Reversible cation/anion extraction from K2La2Ti3O10: Formation of new layered titanates, KLa2Ti3O9.5 and La2Ti3O9

A new soft-chemical transformation of layered perovskite oxides is described wherein K2O is sequentially extracted from the Ruddlesden-Popper (R-P) phase, K2La2Ti3O10 (I), yielding novel anion-deficient KLa2Ti3O9.5 (II) and La2Ti3O9 (III). The transformation occurs in topochemical reactions of the R-P phase I with PPh4Br and PBu4Br (Ph = phenyl; Bu = n-butyl). The mechanism involves the elimination of KBr accompanied by decomposition of PR4+ (R = phenyl or n-butyl) that extracts oxygen from the titanate. Analysis of the organic products of decomposition reveals formation of Ph3PO, Ph3P, and Ph-Ph for R = phenyl, and Bu3PO, Bu3P along with butane, butene, and octane for R = butyl. The inorganic oxides II and III crystallize in tetragonal structures (II: P4/mmm, a = 3.8335(1) angstrom, c = 14.334(1) angstrom; III: /4/ mmm, a = 3.8565(2) angstrom, c = 24.645(2) angstrom) that are related to the parent R-P phase. II is isotypic with the Dion-Jacobson phase, RbSr2Nb3O10, while III is a unique layered oxide consisting of charge-neutral La2Ti3O9 anion-deficient perovskite sheets stacked one over the other without interlayer cations. Interestingly, both II and III convert back to the parent R-P phase in a reaction with KNO3. While transformations of the R-P phases to other related layered/three-dimensional perovskite oxides in ion-exchange/metathesis/dehydration/reduction reactions are known, the simultaneous and reversible extraction of both cations and anions in the conversions K2La2Ti3O10 reversible arrow KLa2Ti3O9.5 reversible arrow La2Ti3O9 is reported here for the first time.

ChemInform Abstract: Synthesis of Anion-Deficient Layered Perovskites, ACa2Nb3-xMxO10-x (A: Rb, Cs; M: Al, Fe), Exhibiting Ion-Exchange and Intercalation. Evidence for the Formation of Layered Brownmillerites, ACa2Nb2AlO9 (A: Cs, H)

Anion-deficient layered perovskite oxides of the formula, ACa2Nb3-xMxO10-x (A = Rb, Cs; M = Al, Fe) for 0 < x less-than-or-equal-to 1.0, possessing tetragonal structures similar to the parent ACa2Nb3O10, have been synthesized. The interlayer A cations in these materials are readily exchanged with protons in aqueous HNO3 to give the protonated derivatives, HCa2Nb3-xMxO10-x; the latter are solid Bronsted acids intercalating a number of organic amines including aniline (pK(a) = 4.63). The distribution of acid sites in the interlayer region of HCa2Nb2MO9 inferred from n-alkylamine intercalation suggests that oxygen vacancies and Nb/M atoms are disordered in the ACa2Nb2MO9 samples prepared at 1100-1200-degrees-C. Annealing a disordered sample of CsCa2Nb2AlO9 for a long time at lower temperatures tends to order the Nb/Al atoms and oxygen vacancies to produce octahedral (NbO6/2)-tetrahedral (AlO4/2)-octahedral (NbO6/2) layer sequence reminiscent of the brownmillerite structure.

Relaxor characteristics of layered Ba1-(3/2)xLaxBi2Nb2O9 ceramics

Barium lanthanum bismuth niobate Ba1−(3/2)xLaxBi2Nb2O9 (x = 0, 0.05, 0.1, and 0.15) powders have been prepared via solid state reaction route. The monophasic layered perovskite nature of each composition of these was confirmed by x-ray diffraction studies. A continuous decrease in the lattice parameter c of parent BaBi2Nb2O9 with increase in La3+ doping level was noteworthy. A decrease in dielectric constant maximum (εm), a shift in dielectric anomaly to lower temperatures (from 488 to 382 K), and an increase in the diffuseness (γ) (from 1.58 to 1.84) of dielectric anomaly were encountered on increasing x from 0 to 0.15. Vogel-Fulcher analyses showed a decrease in freezing temperature (Tf) (from 157 to 40 K) and an increase in the activation energy (0.53 to 1.12 eV) for frequency dispersion with increase in La3+ content. A downward shift in the peak position of the pyroelectric coefficient with increasing La3+ doping level was observed. The observed changes in the above physical properties were attributed to the increase in A-site chemical heterogeneity as a result of aliovalent La3+ doping on Ba2+ sites and associated A-site vacancy formation.

New organic-inorganic perovskite materials with different optical properties modulated by different inorganic sheets

New organic-inorganic perovskites with different PbBr perovskite sheets stabilized by 3- or 4-an-tidinopyridine were synthesized and structurally characterized. 4-Amidinopyridine constructs < 001 >-oriented perovskite with inorganic sheets made up of typical corner-sharing octahedra of PbBr2. Analogous chemistry in the presence of 3-amidinopyridine under the same conditions results in an unusual hybrid perovskite with the inorganic sheets showing a novel framework including both corner-sharing and edge-sharing PbBr2, which is different from any previously reported ones.

Novel < 110 >-oriented organic-inorganic perovskite compound stabilized by N-(3-aminopropyl) imidazole with improved optical properties

In the organic-inorganic perovskites family, the < 100 >-oriented type has been extensively investigated as a result of its unique magnetic, optical, and electrical properties, and only one type of < 110 >-oriented hybrid perovskite stabilized by methylammonium and iodoformamidinium cations or the latter themselves has been known so far. In this paper, another novel < 110 >-oriented organic-inorganic perovskite (C6H13N3)-PbBr4 (compound 1) has been prepared by reacting N-(3-aminopropyl)imidazole (API) with PbBr2 in hydrobromic acid. The crystal structure is determined, which indicates that the perovskite is stabilized by API. The introduction of the optically active organic ligand API into the hybrid perovskite results in a red shift and a great enhancement of photoluminescence in the perovskite with respect to organic ligand API itself. These results have been explained according to calculation based on density-functional theory. Moreover, the excellent film processing ability for the perovskite (C6H13N3)PbBr4 together with the improved optical properties makes it have potential application in optoelectronic devices.

Synthesis and structure of some interesting oxides of bismuth

Synthesis and structures of several new oxides containing bismuth are described. Three types of structures are common among the multinary oxides containing trivalent bismuth. They are the sillenite structure of γ-Bi2O3, the layered perovskite structure of Aurivillius phases and the pyrochlore structure. The influence of Bi3+∶6s 2 lone pair electrons is seen in all the three structures. In transition metal oxides containing trivalent bismuth,d o cations (Ti4+, Nb5+, W6+) stabilize the layered perovskite structure, while cations containing partially-filledd orbitals (V4+, Cr3+, Fe3+) favour pyrochlore-related structures. Ferroelectric distortion ofMO6 octahedra of thed o cations seems to play an important role in stabilizing layered perovskite structures.

Evolution of nanocrystalline BaBi2Nb2O9 in Li2B4O7 BaO-Bi(2)O3-Nb2O5 glass system

Transparent glasses and glass nano crystal composites (GNCs) of various compositions in the system (100 - x)Li2B4O7-x (BaO-Bi2O3-Nb2O5) (where x = 10, 20, and 30 in molar ratio) were fabricated via splat-quenching technique. The glassy nature of the as quenched samples was established by differential thermal analyses. X-ray powder diffraction and transmission electron microscopic (TEM) studies confirmed the formation of layered perovskite BBN via a fluorite like phase. TEM studies revealed the presence of 10 nm sized spherical crystallites of fluorite like BaBi2Nb2O9 phase in the glassy matrix of Li2B4O7 (LBO). The influence of composition on the dielectric and the optical properties (transmission, optical band gap) of these samples has been investigated. (c) 2007 Elsevier B.V. All rights reserved.

Evolution of ferroelectric SrBi2Nb2O9 phase in the Li2B4O7-SrO-Bi2O3-Nb2O5 glass system

Glasses of various compositions in the system (100 - x)Li-2 B-4 O-7 - x (SrO-Bi2O3-Nb2O5) (10 less than or equal to x less than or equal to 60) (in molar ratio) were prepared via a conventional melt-quenching technique. The glassy nature of the as-quenched samples was established by Differential Thermal Analyses (DTA). X-ray powder diffraction (XRD) and Transmission Electron Microscopic (TEM) studies confirmed the amorphous nature of the as quenched and crystallinity in the heat-treated samples. The formation of nanocrystalline layered perovskite SrBi2Nb2O9 (SBN) phase, in the samples heat-treated at temperatures higher than 550degreesC, through an intermediate fluorite phase in the LBO glass matrix was confirmed by both the XRD and High Resolution Transmission Electron Microscopy (HRTEM). The samples that were heat-treated at two different temperatures, 550 and 625degreesC, (containing 0.35 and 0.47 mum sized SBN crystallites) exhibited broad dielectric anomalies in the vicinity of ferroelectric to paraelectric transition temperature of the parent SBN ceramics. A downward shift in the phase transition temperature was observed with decreasing crystallite size of SBN. The observation of pyroelectric and ferroelectric properties for the present samples confirmed their polar nature.

Reaction of La2CuO4 with binary metal oxides in the solid state: Metathesis, addition, and redox metathesis pathways

Investigation of the reaction of La2CuO4 with several binary metal oxides in the solid state at elevated temperatures has revealed three different reaction pathways. Reaction of La2CuO4 with strongly acidic oxides such as Re2O7, MoO3, and V2O5 follows a metathesis route, yielding a mixture of products: La3ReO8/La2MoO6/LaVO4 and CuO. Oxides such as TiO2, MnO2, and RuO2 which are not so acidic yield addition products: La2CuMO6 (M = Ti, Mn, Ru). SnO2 is a special case which appears to follow a metathesis route, giving La2Sn2O7 pyrochlore and CuO, which on prolonged reaction transform to the layered perovskite La2CuSnO6. The reaction of La2CuO4 with lower valence oxides VO2 and MoO2, on the other hand, follows a novel redox metathesis route, yielding a mixture of LaVO4/LaCuO2 and La2MoO6/Cu, respectively. This result indicates that it is the redox reactivity involving V-IV + Cu-II --> V-V + Cu-I and Mo-IV + Cu-II --> Mo-VI + Cu-0, and not the acidity of the binary oxide, that controls the nature of the products formed in these cases. The general significance of these results toward the synthesis of complex metal oxides containing several metal atoms is discussed.

Transmission electron microscopy study of domain structures in ferroelectric SrBi2Nb2O9 ceramics

A transmission electron microscopy study has been carried out on the domain structures of SrBi2Nb2O9 (SBN) ferroelectric ceramics which belong to the Aurivillius family of bismuth layered perovskite oxides. SBN is a potential candidate for Ferroelectric Random access memory (FeRAM) applications. The 90° ferroelectric domains and antiphase boundaries (APBs) were identified with dark field imaging techniques using different superlattice reflections which arise as a consequence of octahedral rotations and cationic shifts. The 90° domain walls are irregular in shape without any faceting. The antiphase boundaries are less dense compared to that of SrBi2Ta2O9(SBT). The electron microscopy observations are correlated with the polarization fatigue nature of the ceramic where the domain structures possibly play a key role in the fatigue- free behavior of the Aurivillius family of ferroelectric oxides.

层状钙钛矿结构化合物的合成、电性和磁性的研究

近年来，随着金属多层膜，磁隧道结和钙钦矿锰氧化物等材料中磁阻现象的发现，以研究磁阻效应的机理和应用为目的的磁电子学迅速发展。这其中钙钦矿结构的稀土锰氧化物以其超大的磁阻值和丰富的物理内涵而备受瞩目。尽管人们对此已做了大量的工作，但是对这类氧化物的深入认识直至超大磁电阻效应物理机制的合理解释仍需做艰苦细致的努力。本论文选择层状钙钦矿稀土锰氧化物作为研究对象，系统地研究了A位，B位的变化和B位原子之间的相互作用对氧化物的结构、磁性和磁阻性质的影响。希望得到钙钦矿中磁、电性质和磁阻与结构之间的关系，能对该系列化合物中电、磁性质的变化规律和相互作用机理作出合理的解释。基于LaSr2Mn2O7的结构特殊性，我们选择了它作为母体化合物。并通过过渡金属离子Cr，Ti，Ni，Fe对Mn离子取代来研究B位原子的变化对性质的影响。结果发现，Cr3＋因为与Mn4＋具有相同的电子形态而能够参与双交换作用，使掺杂Cr3＋的系列样品的磁化强度随cr含量的增加而增加。而掺杂讨＋，Ni2＋，Fe3＋离子的化合物虽然与Mn离子之间的相互作用各不相同，但引起的磁性变化却是相同的。这四种元素的掺杂都提高了体系的磁阻和电阻率。通过对这几种过渡金属取代的比较，发现在LaS2Mn2O7中对Mn离子进行取代的离子和Mn离子之间的交换作用对磁性质的影响并不起主要作用，掺杂引起的主要作用是致使Mn位的无序度增加和对双交换作用的稀释和阻碍。值得注意的是每个系列样品中都有一个样品的磁阻在高温时出现较大的正值，且随着温度的降低转变为负值。例如，在Fe掺杂的系列样品中，只有x＝0.2的样品表现出正磁阻，且MR在28OK时达到74％。这可能是因为掺杂导致的结构变化引起的。这种正磁阻对材料的应用意义重大。电荷有序对磁阻材料是一种很重要的状态，为了提高LasrZMn2O7的电荷有序温度，我们选择了具有孤对电子的Bi3+来取代Sr2+。结果发现，单相样品只能持续到x≤0.2。样品的电荷有序温度并没有象预想的那样有所提高。这是因为体系的二维结构抑止了Bi3＋离子的作用，同时由于体系中Bi3＋的含量较少没有达到提高电荷有序温度的程度。但Tco降低的程度相对于其它离子的取代效果（如Gd）要低。目前n=3的层状钙钦矿研究较少，但是由于该化合物具有结构可变性和理论上可以解释磁转换机理，我们对（La，ca）4kMn3O10进行了深入的研究。在La3-3xCa1＋3xMn3O10（0.5≤x≤1.0）中随La3＋含量的减少，该系列化合物经历了从铁磁性到顺磁性再到反铁磁性的转变，同时在磁阻上也经历了由负磁阻（x＝0.5～0.7）到正磁阻（x=0.8-1.0）的转变。根据磁性和电性的变化规律，我们认为这种正负磁阻的转变是由于体系中超交换和双交换作用的相互竞争引起的。La3＋含量多时，Mn3十离子含量较多，双交换作用占主导地位，产生负磁阻；随着Mn3+离子含量的减少，双交换作用逐渐减弱，Mn4+离子之间的反铁磁性超交换作用逐渐增强，产生了正磁阻。在低掺杂浓度时LaxCa4-xMn3O10（x＝0-0.9）经历了顺磁性到反铁磁性的转变，为了了解其磁性变化过程，我们进一步研究了富含Mn4＋的这一区间。发现磁化强度在x≤0.2的范围内随x增加而增强，在高于0.2的掺杂范围后随x的增加而逐渐降低。这是因为这一区间的磁结构由基态时的G型-AFM向x＝0.9时的C型-AFM的转变。而且这种转变与载流子浓度密切相关。

Synthesis, structure and optical properties of new organic-inorganic haloplumbates complexes (C5H10N3)PbX4 (X = Br, Cl), (C2H2N4)PbBr3

Layered organic-inorganic composite materials (C5H10N3)PbX4 (X = Br 1, Cl 2) containing histaminium dications were grown via a solution-cooling process, and their structure and optical properties were determined. The organic ligand-histaminium introduced into the corner-sharing octahedra of the 'PbX4- layer' contains both primary ammonium and imidazolium different from the traditionally primary amine found in this system. As comparison, another analogous amine of 3-amino-1,2,4-triazol was used as ligand to coordinate with PbBr2 in acid solution. A novel complex (C2H2N4)PbBr3 (3) was obtained with zigzag PbBr2 chains different from the PbX4 layer in compound as 1 and 2. The hybrid (C5H10N3)PbX4 show exciton absorption at 339 nm for X = Cl and 419 nm for X = Br with the corresponding emission at 360 and 436 nm, respectively. The different PbBr2 chain structure of compound 3 does not show photo luminescence.

Synthesis, structure and optical properties of different dimensional organic-inorganic perovskites

By varying the substituent position of aminomethyl on pyridine ring in acid solution, different dimensional lead bromide frameworks ranging from zero-dimension and one-dimension to two-dimension were obtained. 2-(Aminomethyl)pyridine (2-AMP) or 3-(aminomethyl)pyridine (3-AMP) and PbBr2 construct hybrid perovskites, of which (H(2)2-AMP)PbBr4 (1) exhibits two-dimensional perovskite sheets with special hydrogen bonds and (H(2)3-AMP)PbBr6 (2) shows an uncommon zero-dimensional inorganic framework with isolated octahedra. The characteristic exciton peaks in absorption spectra are located at 431 nm for compound 1 and at 428 nm for compound 2. (H(2)4-AMP)PbBr4 (3) with one-dimensional zigzag edge-sharing octahedral PbBr(4)(2-)chains can be obtained using 4-(aminomethyl)pyridine (4-AMP) as organic component under the same experimental conditions as those for 2-AMP and 3-AMP.

Orbital ordering in Cs2AgF4 from first principles

First-principles calculations using the augmented plane wave plus local orbital method, as implemented in the WIEN2K code, have been used to investigate the structural, electronic, and magnetic properties of the layered perovskite Cs2AgF4. Our calculations indicate that an orthorhombic ground state for Cs2AgF4 is energetically favored over tetragonal. We also find that Cs2AgF4 should be a strong two-dimensional ferromagnet, with very weak antiferromagnetic coupling between the layers, in agreement with the experiment. More importantly, an antiferrodistortive ordering of z(2)-x(2) and z(2)-y(2) orbitals is inferred from the density of states and from a spin density isosurface analysis.

Phase behavior of rare earth manganites

Among complex oxides containing rare earth and manganese BaLn(2)Mn(2)O(7)( Ln = rare earth) with the layered perovskite type and Ln(2)(Mn, M)O-7 with pyrochlore-related structure were studied since these compounds show many kinds of phases and unique phase transitions. In BaLn(2)Mn(2)O(7) there appear many phases, depending on the synthetic conditions for each rare earth. The tetragonal phase of so-called Ruddlesden-Popper type is the fundamental structure and many kinds of deformed modification of this structure are obtained. For BaEu2Mn2O7 at least five phases have been identified from the results of X-ray diffraction analysis with the space group P4(2)/mnm, Fmmm, Immm and A2/m in addition to the fundamental tetragonal I4/mmm phase. In the pyrochlore-related type compounds, Ln(2)Mn(2-x)M(x)O(7)(M = Ta, Nb, W etc), there also appear several phases With different crystal structures. With regard to every rare earth, Ln(2)MnTaO(7) phase is stable only for excess Ta and can be obtained under high oxygen partial pressure process. This group has trigonal structure with zirkelite type ( P3(1)21 space group).