High-resolution electron microscopy and X-ray diffraction study of intergrowth structures in α- and β-type YbAlB4 single crystals

Structural features of layered boride YbAlB₄ single crystals with YCrB₄-type (α-type) and ThMoB₄-type (β-type) phases derived from a hexagonal AlB₂-type structure were investigated by electron diffraction, high-resolution electron microscopy and X-ray diffraction. X-ray diffraction experiments indicate the existence of some structural motifs. High-resolution images clearly show that the structural motifs build the intergrown lamellar structures in the matrix. The lamellar structures can be characterized by a coherent tiling of deformed Yb hexagons, which are a common structure unit in the α- and β-type structures. The characteristic intergrown nanostructure is similar to that observed in the β-type TmAlB₄ polycrystalline sample.     

Ca2PbGa8O15: Rational Design,Synthesis, and Structure Determination of a Purely Tetrahedra‐Based Intergrowth Oxide

Intergrowth oxides, like Aurivillius, Ruddlesden–Popper phase, comprise functional layers and exhibit interesting physical properties. The hitherto known intergrowth structures mainly were composed of closed‐packing of oxygen ions, and it is very challenging to develop new types of intergrowth structures. We proposed the possible match between the tridymite and grossite, both of which are purely tetrahedra‐based structures. We synthesized Ca₂PbGa₈O₁₅ ((Ca_0.5Pb_0.5Ga₂O₄)₂(CaGa₄O₇)) and its structure was solved by ab‐initio method. Pb²⁺ is vitally important to stabilize this first example of tetrahedra‐based intergrowth oxide. The appropriate size difference between Pb²⁺ and Ca²⁺ causes the layered type cationic ordering, and reduced the thermodynamic potential, in addition, the high hybridization between Pb 6s6p and O 2p orbitals further consolidate the covalency of the tetrahedra‐base framework.     

Mechanism of aggregation and intergrowth of crystals during bulk crystallization from solutions

Available literature data on aggregation kinetics of crystals of a number of salts during their bulk crystallization from solutions have been analysed. The proposed earlier mechanism of aggregation and intergrowth of crystals during bulk crystallization owing to formation of nucleus‐bridges between crystals was tested and confirmed. The aggregation kinetics of crystals was described by the familiar Smoluchowski equation for coagulation of colloidal particles. However, in a bulk crystallization process, the aggregation constant in this equation decreased as supersaturation in a solution lowered. An expression for the aggregation constant in this equation was proposed. The proposed mechanism of crystal intergrowth duringt bulk crystallization allowed evaluating the specific surface energy of tested salts, which turned out to be in reasonable agreement with published literature data. It was concluded that the intergrowth of crystals during bulk crystallization from solutions proceeded via formation of nucleus‐bridges between crystals. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

CeO2 和 γ-Al2O3 混合氧化物的共生共存效应

 采用改进的柠檬酸络合法合成了 Ce-Al-O 两相氧化物, 并运用 X 射线衍射、X 射线光电子能谱、27Al 魔角核磁、N2 吸附-脱附和储氧量测定等手段对样品进行了表征. 结果表明, 两相共生时 CeO2 和 γ-Al2O3 间发生了强相互作用, 相互调变了彼此的存在状态和微观结构, 抑制了两物相晶粒的长大, 从而提高了 γ-Al2O3 的高温水热老化稳定性, 并使 Ce-Al-O 体系两相氧化物的储氧能力比单相的纳米 CeO2 提高了 2~3 倍, 即使在高温水热处理后样品仍保持很高的储氧性能.     

Unit-cell intergrowth of pyrochlore and hexagonal tungsten bronze structures in secondary tungsten minerals

Structural relations between secondary tungsten minerals with general composition A_x[(W,Fe)(O,OH)₃]_·yH₂O are described. Phyllotungstite (A=predominantly Ca) is hexagonal, , , space group P6₃/mmc. Pittongite, a new secondary tungsten mineral from a wolframite deposit near Pittong in Victoria, southeastern Australia (A=predominantly Na) is hexagonal, , , space group P-6m2. The structures of both minerals can be described as unit-cell scale intergrowths of (111)_py pyrochlore slabs with pairs of hexagonal tungsten bronze (HTB) layers. In phyllotungstite, the (111)_py blocks have the same thickness, 6 Å, whereas pittongite contains pyrochlore blocks of two different thicknesses, 6 and 12 Å. The structures can alternatively be described in terms of chemical twinning of the pyrochlore structure on (111)_py oxygen planes. At the chemical twin planes, pairs of HTB layers are corner connected as in hexagonal WO₃.     

TS-2微球的形成机理、后处理修饰和催化应用

钛硅分子筛材料是一种优异的选择性氧化反应催化剂,能在温和的条件下活化双氧水,并且只副产水,构建了一系列绿色高效的催化反应体系,已成功地应用于环己酮氨肟化、丙烯环氧化等工业过程.但是,工业上使用的钛硅分子筛通常需要经过成型,这避不可免地引入惰性的粘结剂甚至会造成堵孔,导致催化剂的活性降低.因此,直接合成具有微米尺度的钛硅分子筛材料有望解决上述问题.本文通过控制晶化条件直接水热合成了一种由初级粒子经晶间交叉生长堆积成的TS-2微球,详细考察反应条件,包括季铵盐模板剂的用量、H2O/Si比、醇的存在与否和晶化温度等的影响,发现反应体系保持高的碱度、静态晶化以及体系无醇是TS-2微球形成的关键因素.进一步地对TS-2晶化过程进行详细跟踪考察,发现常规TS-2纳米颗粒与TS-2微球在晶化初期均会形成无定形微球.随着晶化的进行,无定形相晶化成为TS-2纳米晶粒,是一级粒子,相互堆积形成次级粒子.较高的碱度使得TS-2微球的一级粒子以交叉生长的方式堆积,从而保证微球形貌在整个晶化过程中得以保持;而TS-2纳米颗粒中初级粒子以平行的方式堆积,无法保持初始的微球形貌,最终形成纳米尺度的聚集体.扫描电镜和透射电镜照片均证实了TS-2微球中初级粒子成交叉生长的方式堆积.TS-2微球催化剂经模板剂、氯化铵和哌啶组成的混合溶液水热处理,发生了溶解-再晶化过程,外比表面积从148增至176 m2 g-1,介孔孔容从0.16 cm3 g-1升至0.24 cm3 g-1;成功引入介孔的同时,仍能保持TS-2微球形貌以及Ti活性中心的四配位状态.经哌啶混合溶液处理后得到的MS-TS-2-PI在环己酮肟化反应中表现出优于MS-TS-2微球的催化性能,环己酮转化率从18.6%升至91.4%,环己酮肟选择性从86.6%升至97%.再经Na+离子交换可以消除骨架中的Si-OH,增强了骨架的疏水性,进一步地提高了其在环己酮肟化反应中的催化性能;环己酮转化率和环己酮肟选择性均>99%.在环己酮肟化连续反应中,TS-2微球表现出稳定的催化性能,使用寿命达到90 h,与工业TS-1催化剂相当,是一种具有工业前景的催化剂.     

Toward a Unified Approach to the Crystal Chemistry of Aurivillius-Type Compounds: II. Bi7Ti4NbO21, a Case Study

In part I of this paper, a generalized structural model of Aurivillius-type compounds has been presented using a 4D superspace group analysis where Aurivillius structures are considered as cation-deficient perovskites with the general formula AB_1−xO₃. Being essentially composition independent, the model is valid for any Aurivillius-type compounds where x is the only composition-dependent parameter. For any composition, the conventional space groups can be easily derived from a unique superspace group. In this second part, a practical example of a structural refinement using the superspace approach is presented for the compound Bi₇Ti₄NbO₂₁ and compared with a conventional 3D refinement. Similarities with other compositionally flexible systems are discussed.     

Synthesis of Zeolite ZSM-2 Using Zeolite NaX as Seeds

Introduction Oxygen and nitrogen have been produced tradition-ally by cryogenic distillation of air. Methods for the non-cryogenic separation based on selective adsorption have been developed and commercialized since the 1970s and have led to a cost-effective process for this important separation.1 Low-silica zeolites are important materials for producing oxygen by selective adsorption of nitrogen. In 19891990, a new generation of lith-ium-based adsorbents was developed.2,3 Highly lithium exc…     

Effects of Pressure and Temperature on the Formation of Tungsten-Bronze-Related Phases, RExWO3+y, with RE=La and Nd

The influence of pressure (P) and temperature (T) on the formation of tungsten-bronze-related phases containing lanthanum and neodymium was investigated. A large number of samples with bulk compositions RE_xWO₃, prepared by solid-state reaction in the pressure and temperature regions P= 10-80 kbar and T= 1170-1620 K were examined by X-ray powder diffraction and electron microscopy, and a (P-T) diagram showing the phase relations was drawn. Three tungsten-bronze-related phases with perovskite (PTB)-, hexagonal (HTB)- and intergrowth (ITB)-type structures were identified. The PTB bronze RE_xWO₃ with x≈ 0.10 was formed at p≤50 kbar. The HTB-related phase with x≈ 0.10 was observed in samples prepared at P≥20 kbar, whereas phases of (n)-ITB-type were observed only in the 25-50 kbar region. In the latter pressure region, the PTB and ITB phases were only seen in samples prepared at T > 1520 K, while the HTB-related phase was found in almost all samples. The HTB- and ITB-related compounds are metastable, probably fully oxidized, high-pressure phases of composition RE_xWO_3+3x/2 with x≤0.13. They transform to a cubic PTB bronze during annealing in inert atmosphere under ambient pressure conditions. According to microanalysis studies of individual crystals, less than 40% of the hexagonal tunnel sites in the HTB and ITB structures are occupied by RE³⁺ ions. A superstructure of HTB-type with ≈60% occupancy of the hexagonal tunnel sites (x≈0.20) was observed in a few crystals from the samples prepared at P= 80 kbar. Ordered, defect and intergrowth structures are presented.