Application of MII 2MV 2(acac)2(OMe)12 Derivatives in Sol-Gel Preparation of Oxide and Oxide Nanocomposite Materials for Catalysis

Hydrolysis of M^II ₂M^V ₂(acac)₂(OMe)₁₂, M^II=Co or Ni and M^V=Nb or Ta, in dry toluene, subsequent evaporation of the solvent, and heating to 500°C, provides access to a catalytically active oxide. The thermogravimetry (TG) analyses of the thermal behaviour of the hydrolysed alkoxides show three distinct steps. The first weight loss occurs at 120°C, the second at 390°C, and the third at 480°C. The weight is constant at 67% of original weight from 480 to 900°C. The powder X-ray patterns of the Co-Ta hydrolysed alkoxide show that powder heated to 500°C is amorphous but powder heated to 900°C revealed the presence of an equimolar mixture of Co^IITa₂O₆ and Co₄ ^IITa₂O₉. Gelation and further transformation on thermal treatment were found to occur in the same way for Co₂Ta₂(acac)₂(OMe)₁₂, Ni₂Ta₂(acac)₂(OMe)₁₂, and Co₂Nb₂(acac)₂(OMe)₁₂.Interaction of Co₂Ta₂(acac)₂(OMe)₁₂ solution with NaY 12 Å zeolite was found to be an exothermic reaction providing access to a nanocomposite compound. The latter has been investigated with the aid of EXAFS spectroscopy. The interaction with NaY 12 Å zeolite was found to occur in the same way for Co₂Nb₂(acac)₂(OMe)₁₂.     

Molecular Precursor Role in the Synthesis of ZrMVI2O8, MVI = Mo,W: Isolation and Properties of Zr3Mo8O24(OiPr)12(iPrOH)4

The studies of zirconium isopropoxide solvate, Zr(OiPr)4·iPrOH(I), interaction with molybdenum oxoisopropoxide in different solvents (HOiPr, hexane) revealed I to be the only isolable crystalline product in alcohol. In hexane I crystallized from Zr-rich solutions (up to Zr : Mo = 1 : 2 ratio). From the solutions with Zr : Mo = 1 : 2 ratio repeatedly dried in vacuo and subsequently redissolved in hexane, the crystallization of Zr3Mo8O24(OiPr)12(iPrOH)4(II) occurred slowly with 12% yield. II can be recrystallized from hexane, but is destroyed by iPrOH which causes the formation of I. Thermal decomposition of II in air at 800°C (2 h) gives a single phase ZrMo2O8(III). Hydrolysis studies of hexane solutions, prepared in a manner analogous to those, from which II was obtained, showed that single-phase samples of III could be obtained when a thin layer of solution was left for hydrolysis and evaporation of solvent in a moist air and then annealed at 800°C (2 h). The same kind annealing of a xerogel, obtained by hydrolysis with water solutions in iPrOH and subsequent drying at 100°C gave a complex mixture of phases where III was not even the major component. No Zr-W complex was isolable under analogous conditions. From the xerogel, obtained by hydrolysis with H2O/iPrOH, ZrO2 and WO3 crystallized separately on heating. Only traces of ZrW2O8(IV) were obtained along with individual oxides when 1% water in ether was applied for hydrolysis. Molecular precursor is therefore crucial for obtaining III, IV.     

纳米Al2O3粒子的制备

以异丙醇铝Al(Oprⁱ)₃(即Al(OCH(CH₃)₂)₃)为原料,用醇盐水解法制备纳米氧化铝粒子,比较系统地研究了制备条件(加水方式、反应物配比、浓度、溶剂等)对产物粒子颗粒大小的影响,采用TEM、X射线衍射等技术对所得产品性能进行了表征.实验结果表明,纳米Al₂O₃粒子分散性好,粒径在20-100nm之间,颗粒的形状和尺寸随反应条件的不同而变化.     

无机溶胶凝胶法制取Y2O3纳米微粒

以廉价无机盐为原料，采用溶胶凝胶法制备出尺度均匀，一次颗粒尺寸平均为60nm，颗粒呈球形的高纯Y2O3，纳米微粒。研究发现适量SO4^2-离子的添加对生成前驱物溶胶及煅烧得到球形的Y2O3纳米微粒起关键作用。对前驱物在煅烧过程中的物相变化进行了研究，分析了煅烧温度对产物粒度和纯度的影响，结果表明在不使生成物颗粒过分长大的前提下，升高煅烧温度有助于制取高纯和晶化完全的Y2O3微粉。     

溶胶-凝胶法合成锂离子电池正极材料LiV3O8

锂钒氧化物;扩散系数;溶胶-凝胶法合成锂离子电池正极材料LiV3O8     

Sol-Gel Derived Ferroelectric Thin Films: Avenues for Control of Microstructural and Electric Properties

The paper presents short review of the works performed during the last few years in the field of the alkoxy-derived ferroelectric films. PZT films were prepared using titanium and zirconium alkoxides and Pb(CH₃COO)₂· 2H₂O as precursors. Different way of lead acetate dehydration and the impact of lead excess in the precursor solutions on the properties of the PZT films are discussed. Trimetallic alkoxide systems Bi(OR)₃-Ta(OR)₅-ROH (R = Me, Et or ⁱ Pr) were studied as precursors for preparation of SrBi₂Ta₂O₉ films. Films prepared from these solutions and annealed at the temperature between 700 and 750°C demonstrated the remanent polarization P_r* – P^{^} _r = 7–9 C/cm². Ba_1-xSr_xTiO₃ films we applied from modified alkoxide solutions. Decomposition of the organic phase in the course of thermal treatment of the films is studied by IR-spectroscopy. The dependence of the dielectric permittivity of the films via the annealing temperature is reported. Preparation of LiNbO₃, SrZr_0.2Ti_0.8O₃, Zr_0.8Sn_0.2TiO₄ is briefly discussed.     

Hydrolysis of 1,2-diacetoxypropane by Immobilized Lipase on Cellulose Acetate-TiO2 Gel Fiber Derived from the Sol-Gel Method

Lipase from Rhizomucor miehei was entrap-immobilized on cellulose acetate-TiO₂ gel fiber by the sol-gel method. This fiber-immobilized lipase was stable in a phosphate buffer solution and easy to handle. The enantioselective hydrolysis of 1,2-diacetoxypropane catalyzed by this immobilized lipase could be performed in buffer solution unlike the lipase immobilized on an alginate matrices. The enantioselectivity was improved in presence of this fiber-immobilized lipase compared with the hydrolysis catalyzed by the native lipase. This finding indicates that the active site structure of lipase immobilized on fiber was retained to some extent, though the enzyme conformation may become flexible in presence of water. We also compared the properties of this fiber-immobilized lipase with native lipase and commercially available immobilized lipase from Rhizomucor miehei, viz., Lipozyme.     

Preparation of SrBi2Ta2O9 from Metal Alkoxides

SrBi₂Ta₂O₉ (SBT) has potential application in FERAM. Some problems in the sol-gel processing of SBT, such as the solubility of metal alkoxides, chemical modification with a chelating reagent and crystallization behavior of the gels, are investigated.The starting solutions were prepared with Sr(OC₄H₉)₂, Bi(OC₃H₇)₃, and Ta(OC₂H₅)₅. Ethoxyethanol and acetylacetone (ACAC) were used as solvent and chelating reagent, respectively. Ta- and Bi-alkoxide are chemically modified with ACAC, but Sr-alkoxide was not. The SBT solution was stabilized with ACAC for ca. 3 months. After hydrolysis of the SBT solution with the addition of ACAC, a monolithic and transparent gel was obtained at room temperature in 100 days. The X-ray diffraction peaks of SBT and very weak peaks of SrTa₂O₆ (ST) and SrBi₂O₄ (SB) were found after calcination at 700°C for both of the gels obtained with and without addition of ACAC. In contrast, the stronger peaks of ST and SB were observed for the powder mixture of SrCO₃, Bi₂O₃, and Ta₂O₅ after calcination at 800°C. These results show the better homogeneity of the gels.     

Sol-Gel Preparation of Fast Proton-Conducting P2O5-SiO2 Glasses

We have investigated the proton conductivities of the sol-gel-derived P₂O₅-SiO₂ glass at –50 to 120°C. The obtained glass is porous, where the surface area, pore volume and pore diameter are 740 m²/g, 0.5 cm³/g and <5 nm, respectively. The freezing temperature of water molecules adsorbed in the pores was –20°C, which is much lower than that of free liquid water due to the quantum size effect of the water confined in the pores. The electrical conductivities followed the Arrhenius equation in the temperatures between –20 and 120°C. Below –20°C, the adsorbed-water molecules were frozen, resulting in a rapid decrease of the proton conductivity. Considering the high conductivity, chemical and thermal stability, this oxide glass membranes have potential for the fuel cell membrane.     

Synthesis of Organic-Inorganic Hybrid Materials by Incorporation of Molybdenum and Tungsten Hydrated Oxides in Polymers

In order to obtain new organic-inorganic hybrid materials the method exploiting the phenomenon of polymer crazing was investigated. Polypropylene and polyethyleneterephtalate films were subjected to crazing to achieve high porosity. Incorporation of hydrated oxides of Mo and W in porous polymer matrix was performed by hydrolysis of alkoxides in pores using counterflow diffusion technique. It was shown that peculiarities of the hydrolysis of the initial compounds affect significantly the distribution of substances inside porous polymer matrix and the possibility of accumulation of inorganic component inside the film. Mo matter in contrast to W is easily incorporated in the polymer matrix to form a well-defined layer. These samples demonstrated high photosensitivity.     

Preparation and Characterization of Sol-Gel Derived Y2O3 Thin Films

Sol-gel derived Y2O3 thin films have been prepared on platinum coated silicon wafers and fired to temperatures ranging from 400°C to 750°C. Multiple coats were used to obtain films up to 0.5 m thick with an intermediate firing of 400°C between coatings. Top Pt electrodes were sputtered to form monolithic capacitors. These films exhibited a dielectric constant of 18 and a leakage current of 10–11–10–7 A/cm2, making them attractive candidates for high dielectric constant dielectric films in high density DRAMs.     

Nanostructured pure gamma-Fe2O3 via forced precipitation in an organic solvent

Pure maghemite, gamma-Fe(2)O(3), was prepared as ultra fine particles in the nanometer-sized range via the forced precipitation method in an organic solvent. The precipitation of iron(III) ions, from iron(III) chloride in 2-propanol led selectively to highly dispersed particles of ferrihydrite, which upon treatment with temperatures higher than 200 degrees C under dynamic vacuum resulted in high-surface-area particles of gamma-Fe(2)O(3). Precipitation in water also led to ferrihydrite, but the final product, after heating at 300 degrees C, contained a mixture of gamma-Fe(2)O(3) and alpha-Fe(2)O(3) (hematite). The precipitation from iron(III) nitrate in water resulted in goethite which was converted to hematite upon heating. On the other hand, the final product in 2-propanol was a mixture of maghemite and hematite. The products were characterized by FTIR, TGA, XRD, and gas sorption analysis. Nitrogen gas adsorption studies for the pure gamma-Fe(2)O(3) samples revealed mesoporous particles with high surface areas in the range of 70-120 m(2) g(-1) after heat treatment at 300 degrees C. The gamma-Fe(2)O(3) particles retained their gamma-phase as well as their mesoporous structure at relatively high temperatures, as high as 400 degrees C.     

Sol-Gel Synthesis Route for the Preparation of Y(Ba1−x Sr x )2Cu4O8 Superconducting Oxides

Superconducting oxide ceramics of composition Y(Ba_1–x Sr _x )₂Cu₄O₈ (x = 0.00, 0.10, and 0.20) have been prepared by a simple sol-gel method based on the complexation of metal ions in aqueous medium, by chelating acetate and tartarate ligands. Homogeneous sols were obtained by complexing copper ions with tartaric acid, which prevented the flocculation of copper acetate during the gelation process. Single-phase bulk samples were obtained after firing the mixed-metal polymeric acetate-tartarate precursor to 835°C for 70 h in flowing oxygen atmosphere. Thermal decomposition of the gels was studied by thermogravimetry. Effect of strontium substitution on the properties of the compounds was studied by X-ray powder diffraction, electron microscopy, X-ray photoemission spectroscopy and resistivity measurements. These data indicate that nearly monophasic Y(Ba_1–x Sr _x )₂Cu₄O₈ superconducting samples were obtained for x < 0.30. The Sr-doping in the YBa₂Cu₄O₈ (Y-124) phase shows a pronounced effect on the superconducting properties enhancing the critical temperature from 78 K (for the non-substituted sample) to 88 K (for Y(Ba_1–x Sr _x )₂Cu₄O₈).     

溶胶-凝胶法制备SrBi2Ta2O9铁电陶瓷薄膜

溶胶-凝胶法制备SrBi2Ta2O9铁电陶瓷薄膜     

New Gelation Process for Pt/Al2O3 Catalysts Preparation

Gel of platinum and aluminum was prepared by an anhydrous gelation process using a mixture of aluminum sec butoxid, platinum acetylacetonate and Butanol-2. The investigation of this gelation by FTIR, UV-vis and ²⁷Al NMR spectroscopies suggest that a slow polymerization of aluminum precursors occurs according to an etheration mecanism likely catalysed by metallic platinum which could be formed by the reduction of platinum in Pt(acac)₂ by sBuOH in the mixture during aging.     

Li2Mg2Si4O10F2、H2Mn8O16•1.4H2O和Li1.3Ti1.7Al0.3(PO4)3在高浓度LiCl水溶液中的离子交换行为

研究了用功能材料Li2Mg2Si4O10F2 (LHT)、H2Mn8O16•1.4H2O (CRYMO)和Li1.3Ti1.7Al0.3(PO4)3 (LTAP)分别去除高浓度氯化锂水溶液中的杂质Fe3＋、K＋和Na＋.实验结果表明，这几种功能材料分别对溶液中的杂质Fe3＋、K＋和Na＋有很高的选择性，除杂效果明显.分析和研究了这几种功能材料在高浓度氯化锂水溶液中分别与Fe3＋、K＋和Na＋的交换行为.结果表明，在高浓度氯化锂溶液中这几种功能材料与杂质交换的动力学行为可近似用JMAK方程描述.     

纳米Cu2O/珍珠贝壳复合光催化材料的制备及其在有机染料处理中的应用

将珍珠贝壳废弃物活化并作为载体,应用原位水解法制备出Cu2O/珍珠贝壳复合材料.运用X射线衍射、X射线光电子能谱、扫描电镜、紫外-可见漫反射吸收光谱对复合材料进行表征.用活性大红染料B-3G水溶液作为模拟废水评价复合材料在可见光下的催化性能.结果表明,负载的Cu2O呈椭球形,理论平均粒径为16.8nm.复合材料对紫外和...     

Preparation of Gold Microcrystal-Doped TiO2, ZrO2 and Al2O3 Films Through Sol-Gel Process

Au-microcrystal-doped TiO₂, ZrO₂ and Al₂O₃ films were made by sol-gel dip-coating method using titanium, zirconium and aluminum alkoxides with HAuCl₄ · 4H₂O. The influence of the oxide matrix composition on the maximum amount of the Au microcrystals that can be incorporated in the oxide film was examined. Some amount of Au microcrystals were exhausted to the surface of Au microcrystal-doped oxide films when an excess amount of HAuCl₄ · 4H₂O was dissolved in the coating solution. The maximum amount of Au that can be incorporated in the oxide film was found to increase with the increase of the pH point at zero charge (PZC) of the matrix oxide. This should be due to the fact that AuCl ₄ ^- ions are charged negative and also Au microcrystals tend to charge negative, so that the oxide gel with high PZC, which has a tendency to charge positive, may fix the ions and/or microcrystals to its interior. A maximum amount of Au microcrystals as high as 12.6 vol% was attained in an Au:Al₂O₃ film.     

溶胶-凝胶法制备用于CO2气氛下乙苯胶氢反应的高活性Cr2O3-SiO2催化剂

苯乙烯是石化工业中十分重要的化学品,全世界每年生产大约 1300 万吨苯乙烯,其中有90%的苯乙烯是在大量过热水蒸气存在下,于550～650 ℃由乙苯在铁-钾基催化剂上脱氢制得的. 该工艺受热力学平衡限制,并且由于采用大量过热的水蒸气和较高的反应温度而能耗很高,因此人们一直试图寻找新的替代工艺. 最近,利用CO2作为温和氧化剂进行乙苯脱氢制苯乙烯引起人们浓厚的兴趣[1～3]. 利用CO2进行乙苯脱氢能够大幅度降低能耗,并且提高苯乙烯的平衡收率[4]. 但是,现行乙苯脱氢传统工艺中使用的铁-钾基催化剂在CO2气氛下不能有效地催化乙苯脱氢,因此有必要寻找适合这一新工艺的高性能催化剂. 人们已经研究了CO2气氛下各种氧化物催化剂上的乙苯脱氢反应,在这些催化剂中,氧化铬和氧化钒表现出较好的催化性能.     

Gd2O3:Eu3+ X射线溶胶-凝胶发光薄膜的制备与表征

高分辨率X射线成像系统要求其发光材料同时具有X射线截止本领强、光产额高、余辉短以及与光电器件波长匹配好等特性. Gd2O3:Eu3 因其优越的发光性能和Eu3 红光发射等优点而在高能射线激发发光材料中占有重要地位. 近几年发展起来的透明X射线薄膜发光材料具有更高的衬度和空间分辨率、热传导率、均匀性和附着力等优点[1], 因而有望成为取代传统荧光粉的新一代X射线成像材料. 在各种薄膜制备工艺中, 溶胶-凝胶法以其价格低廉、工艺简单、制备温度低、均匀性好、可实现微量掺杂等优点而日益受到人们重视, 通过该方法并辅以适当的后处理工艺可制备出透明、致密的薄膜.