纳米／微米结构氧化物材料的水热合成、形貌与发光性质研究

采用水热法结合后续热处理制备了一系列纯的和稀土离子（Eu3＋，Dy3＋）掺杂的黔具有纳米／微米结构的无机氧化物材料，包括YB03、姚03、Ga203和硅基MCM一攀41介孔分子筛体系。研究了这些体系的水热产物的晶体形貌、结构以及它们的生乖～一＿长机理，并通过进一步热处理得到了保持水热产物纳米／微米结构形貌的发光材料，报道了以上各个体系材料的光致发光性能。一把姚03和Eu203粉末直接加入H3Bo3水溶液中，调节pH一1一4，在180一270夸＿少℃水热处理得到了具有vaterite结构的YBo3：Eu3＋晶体。xRD和FEsEM结果证明一扭03：E矿"晶体是由厚度小于50nm的纳米晶片构成的花状和猴头菇状的微米级晶丫体。水热温度提高时纳米晶片的厚度没有增加，形貌也不变，但是结晶度和发光一强度有所提高。pH值对纳米晶片之间的距离、角度和晶片数量有影响。pH低时，纳米晶片更多且包裹得更紧，形成了猴头菇状；而pH高时，晶片分得更开一些呈花朵状。这与pH值低时结晶成核较快较多有关。YB03：E矿＋水热和固相法样品在24Onm激发下的发光谱峰位相同。但水热样品比固相法样品具有较高的红橙比［Eu3＋：I（，D。一7F2）／I（SD。一7FI）］，增加了12一37％。在24oC下制备的花03：Eu3＋水热样品具有最大的结晶度和发光强度。报道了三种晶形调节剂对水热晶体形貌的影响结果。硝酸钻水溶液用氨水调节至pH一8一n，200oC下水热处理24小时，产物经xRD确定是单斜晶系的碱式硝酸盐叽O（0H）9困03）。FEsEM观察发现产物是一种具有几＿三叶形截面的棱柱。改变合成条件可以调节三叶形棱柱的尺寸。增加氨水量时，PH从8调到n后，棱柱直径可从微米级调节到亚微米级，即从3一5林m左右下降到200一300纳米，同时长径比也有所增加，从pH一8的5增加到pH＝n的10。调节机制可解释为较高的pH条件下结晶成核作用进行较快，形成了更多的晶核。三叶形棱柱的生长机理是、O（OH）9困03）的晶核依靠内在的趋势长成棒状纳米粒子；并通过一种直接的聚集生长，这些起始的纳米棒沿着它们横截面的径向方向快速自堆积成一种Y型结构的棒束；然后沿着棱柱轴向和平行于棱柱叶片方向的晶面同时优先生长，而垂直于叶片方向上的晶面生长得相对缓慢，导致三叶形棱I、－纳米／微米结构氧化物材料的水热合成、形貌与发光性质研究柱的形成。、经过高温相转变得到了姚03三叶形棱柱。采用同样方法可以制得姚03：E矿＋的三叶形棱柱发光粉，其光谱与固相法样品的一致。将Gacl3一HZO一NaOH体系在pH＝6一8时于180℃下水热处理得到了正交晶系的Gao0H晶体，其形貌分别是宽度在200一30Onm之间长径比约1：7的四方棱柱（pH＝6）和长径比约1：3纺锤状的纳米棒束（pH＝8）。使用HZO／DEG混合溶剂可以增加棱柱的长径比，1：Ivol时增加到1：15；1：Zvol时获得的是长达几十微米的四方棱柱纳米线6Go0OH纳米棒是从最初的胶状沉淀中成核后沿着c轴优先生长而成的。pH值的高低可导致Ga0OH晶体从四方棱柱到纳米棒束的不同形貌。DEG的存在对晶体的生长可能有两点作用：一是抑制晶核形成；二是降低晶体沿着横截面晶面的生长速度。经过高温锻烧的产物是保持着前驱体形貌的p一GaZO3晶体。254nm激发下p一GaZO3纳米棒的发射谱是从300nm到600nln的宽峰，最大值在455nln。发光的平均寿命是64ns。其蓝光发射起源于氧空位给体提供的电子和来自受体嫁空位或者嫁氧空位对的空穴之间的复合。采用相似方法制备了p一GaZO3：Dy纳米棒束，并与固相法样品对比了光谱性质的异同。将三种5102基材料：MCM一41型分子筛（直接分子筛CMS和萃取分子筛EMS）、无规颗粒（ASP）和干凝胶（SG）进行从室温到1000℃的不同温度不同时间热处理。254nm激发下，MCM一41没有发光现象。而ASP和SG系列样品随着热处理温度不同而显示不同的PL。说明ASP和SG与MCM一41有着不同的发光机理。排除了ASP和SG样品的发光中心是来自5102网络本身的结构缺陷，认为是其中所含有机物在热处理中产生的碳杂质引起。结果也表明MCM41中模板剂在热处理的碳化产物并没有引起MCM一41的PL。在365nm激发下，MCM一41与ASP、SG的PL现象大致相同。表明所有系列的样品的发光机理相同。CMS和EMS两个系列在300℃以上处理的样品的PL相似，说明模板剂的存在及其碳化并没有影响MCM一41的PL。所有系列样品在365nm激发下的PL认为是起源于5102网络中与氧相关的结构缺陷三Si一0．，而不是碳掺杂作用引起的。

Field emission from TiO2/Ti nanotube arrays with different morphologies

Well-aligned TiO2/Ti nanotube arrays were electrochemically formed in a HF solution for different anodization times. Field emission scanning electron microscopy (FE-SEM) images reveal that anodization time had a great influence on the morphology of TiO2/Ti nanotube arrays. The composition of resulting nanotubes was analyzed by X-ray photoelectron spectroscopy (XPS). Field emission properties of the prepared samples with different morphologies were investigated by the Fowler-Nordheim (F-N) theory. The results indicate that the morphology can affect field emission behaviors. TiO2/Ti nanotube arrays with clear, uniform, and short nanotubes display moderate field emission properties, and have the better turn-on field of 4.6 V/mu m and good field emission stability. (C) 2010 Elsevier B.V. All rights reserved.

Preparation of A-type zeolite membranes on nonporous metal supports by using electrophoretic technique

A-type zeolite membranes were prepared on the nonporous metal supports by using electrophoretic technique. The as-synthesized membranes were characterized by XRD and SEM. The effect of the applied potential on the formation of the A-type zeolite membrane was investigated, and the formation mechanism of zeolite membrane in the electric field was discussed. The results showed that the negative charged zeolite particles could migrate to the anode metal surface homogenously and rapidly under the action of the applied electric field, consequently formed uniform and dense membranes in short time. The applied potential had great effect on the membrane formation, and more uniform and denser zeolite membranes were prepared on the nonporous metal supports with 1 V potential.

Assembly of the highest connectivity Wells-Dawson polyoxometalate coordination polymer: the use of organic ligand flexibility

Through tuning the length of flexible bis(triazole) ligands and different metal ion coordination geometries, four Wells-Dawson polyoxoanion-based hybrid compounds, [Cu-6(btp)(3)(P2W18O62)] center dot 3H(2)O (1) (btp = 1,3-bis(1,2,4-triazol-1-yl)propane), [Cu-6(btb)(3)((P2W18O62) center dot 2H(2)O (2), [Cu-3(btb)(6)(P2W18O62)] center dot 6H(2)O (btb = 1,4-bis(1,2,4-triazol-1-yl)butane) (3), and [Cu-3(btx)(5.5)((P2W18O62) center dot 4H(2)O (btx = 1,6-bis(1,2,4-triazol-1-yl)hexane) (4), were synthesized and structurally characterized. in compound 1, the metal-organic motif exhibits a ladder-like chain, which is further fused by the ennead-dentate [P2W18O62](6-) anions to construct a 3D structure. In compound 2, the metal-organic motif exhibits an interesting Cu-btb grid layer, and the ennead-dentate polyoxoanions are sandwiched by two Cu-btb layers to construct a 3D structure

Photo- and Thermo-Chromic Study of the Ethylenediamine Trimolybdate

The ethylenediamine trimolybdate (ENTMo) can show unusually photochromic and thermochromic properties and there exists in the difference of chromic mechanisms, which has been proved in our previous work [I]. In this paper, X-ray powder diffraction (XRD), Fourier transform infrared (FTIR) and laser Raman spectroscopy (LRS) of the colored samples are characterized and analyzed in detail. The crystal structure, the inorganic skeleton and the microenvironment of center ions of the colored samples do not substantively change except distortion. The color difference of the photochromic and the thermochromic samples is discussed and that the difference of reduction sites result in their different chromic mechanisms is suggested.

Rectangular AgIn(WO4)(2) nanotubes: A promising photoelectric material

Rectangular AgIn(WO4)(2) nanotubes with a diameter range of 80 to 120 nm and length up to 2 mu m have been synthesized by a hydrothermal method. These nanotubes exhibit interesting white light emissions when using 320 nm as the excitation wavelength. A photocatalytic reaction for water decomposition to evolve K, was performed under UV irradiation, and the rate of H, evolution is nearly seven times that of the sample prepared by a solid-state reaction, which shows much higher photocatalytic activities compared with their bulk counterparts.

Two-dimensional beta-NaLuF4 hexagonal microplates

A simple hydrothermal method has been developed to synthesize monodisperse beta-NaLuF4 microplates in a large scale. The microcrystals have a perfect hexagonal shape with a diameter of about 5.2 mu m and a thickness of 300 nm. Trisodium citrate (Cit(3-)), which is introduced into the reaction mixture and acts as the chelating agent and shape modifier, plays a key role in fine-tuning the microstructures. The dominant adsorption of Cit(3-) onto the {0001} facets lowers the surface energy of these facets.

Template-free, surfactantless route to fabricate In(OH)(3) monocrystalline nanoarchitectures and their conversion to In2O3

In this work, a one-dimensional microrod-based three-dimensional flowerlike indium hydroxide (In(OH)(3)) structure was fabricated, without any templates or surfactants, using a well-known hydrothermal approach at a non-high temperature. In2O3 with similar morphology was formed by annealing In(OH)3 precursors and was characterized by Raman spectrum and photoluminescence (PL) spectrum in detail.

Self-assembled 3D microflowery In(OH)(3) architecture and its conversion to In2O3

Using sodium dodecyl sulfate (SDS), a 3D microflowery indium hydroxide [In(OH)(3)] structure assembled from 2D nanoflakes was fabricated in a large quantity via a hydrothermal approach at relative low temperature. The obtained In(OH)(3) flowers exhibited a narrow size range between 4 and 6 mu m. The properties of these composites were characterized by XRD, EDX, FE-SEM, TEM, SAED, and TGA. In this work, both the use of urea and SDS and the amounts of these components played important roles in the formation of In(OH)3 with different nanostructures.

Constructing porous frameworks from one-dimensional cobalt-oxygen clusters and pyridinedicarboxylate ligands adopting two rare coordination modes

A porous material with cobalt-oxygen cluster framework has been synthesized hydrothermally, which possesses large and rigid channels and manifests strong antiferromagnetic interactions, and the pyridinedicarboxylate ligand exhibits two types of rare coordination modes.

Self-Assembled Growth of Agln(MoO4)(2) Submicroplates into Hierarchical Structures and Their Near-Infrared Luminescent Properties

Layer-controlled hierarchical flowerlike AgIn(MoO4)(2) microstructures with "clean" surfaces using submicroplates as building blocks without introducing any template have been fabricated through a low-cost hydrothermal method. The near-infrared luminescence of lanthanide ion (Nd, Er, and Yb) doped AgIn(MoO4)(2) microstructures, in the 1300-1600 nm region, was discussed and is of particular interest for telecommunication applications. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, electron diffraction, and photoluminescence spectra were used to characterize these materials.

Metal-organic frameworks based on the pyridine-2,3-dicarboxylate and a flexible bispyridyl ligand: syntheses, structures, and photoluminescence

Three new metal-organic coordination polymers, [Cu(2,3-pydc)(bpp)]center dot 2.5H(2)O (1), [Zn(2,3-pydc)(bpp)]center dot 2.5H(2)O (2) and [Cd(2,3-pydc)(bpp)(H2O)]center dot 3H(2)O (3) (2,3-pydcH(2) = pyridine-2,3-dicarboxylic acid, bpp 1,3-bis(4-pyridyl)propane), have been synthesized at room temvperature. All complexes have metal ions serving as 4-connected nodes but represent two quite different structural motifs. Complexes 1 and 2 are isomorphous, both of which feature 2D -> 3D parallel interpenetration. Each two-dimensional (2D) layer with (4, 4) topology is interlocked by two nearest neighbours, one above and one below, thus leading to an unusual 3D motif. Complex 3 has a non-interpenetrating 3D CdSO4 framework with cavities occupied by uncoordinated water molecules.