Formation of Nickel-Zinc Ferrite Embedded in a Silica Xerogel Matrix

We report a study using X-ray diffraction, refinement Rietveld, IR absorption spectroscopy and vibrating sample magnetometry of the formation of particles of Ni-Zn ferrites embedded in a xerogel SiO₂ matrix. Initial solutions were prepared mixing TEOS, distilled water, ethanol, and three different nitrates: iron, nickel and zinc. A molar ratio H₂O:TEOS:Et-OH of 11.66:1.0:4.0 was used in all solutions. Formation of Ni_0.5Zn_0.5Fe₂O₄ as well as structural modifications of the SiO₂ matrix induced by these particles are discussed. Ni-Zn crystals having dimensions varying from 4 to 16.5 nm have been synthesized by a suitable heat treatment schedule at temperatures varying from 700 to 1100°C. The coercivity values for different heat-treated samples are found in the range 11–193 Oe, which are significantly larger than those presented by bulk Ni-Zn ferrites.     

In-situ Synthesis of Copper Phthalocyanine in Silica Xerogel Matrix

Using a newly developed in-situ syntheses technique during sol-gel process, copper phthalocyanine (CuPc) is synthesized in-situ in silica xerogel matrix homogeneously. It has been confirmed by UV-Vis and IR spectroscopies that the copper ions which existed in the form of complex-ions [Cu(H₂O)₄]²⁺ and [CuCl₄]^2– in the stages of sol and wet gel were destroyed in the heat treatment process, meanwhile the copper phthalocyanine molecules were synthesized in-situ gradually during the wet gel to xerogel transition. The dimerization phenomenon of CuPc in the composite is suppressed greatly because the in-situ synthesized CuPc molecules were well isolated in the micro-pores of the xerogel matrix. The doping concentration of Copper phthalocyanine in sol-gel derived matrix can be enhanced also by this in-situ synthesis method.     

Structure Control in Sol-Gel Silica Synthesis Using Ionene Polymers. 2: Evidence from Spectroscopic Analysis

By use of the Menshutkin reaction a variety of polyviologens have been synthesised containing bromide or tosylate counter-ions and varying numbers of methylene units. These ionene polymers have been shown to display lyotropic liquid crystalline behaviour. The effects of these polyviologens on the structure of growing silica networks synthesised using the sol-gel method were studied by spectroscopic analysis. Depending on the concentration, the type of polyviologen and whether a lyotropic liquid crystalline phase was used, evidence for an effect of these polymers on silica structure was observed using FTIR and ¹H NMR spectroscopies. The presence and strength of an absorption band at 550 cm^–1 (coupled with an absorption at 450 cm^–1) was suggestive of some ordering occurring in these materials. Additionally, possible evidence of specific interactions involving the water molecules was obtained from ¹H NMR spectroscopy.     

Cobalt Oxide/Silica Xerogels Powders: X-Ray Diffraction,Infrared and Visible Absorption Studies

Using x-ray diffraction, infrared and visible absorption spectroscopies we have studied: silica xerogel powders when cobalt nitrate is incorporated and mainly the evolution of the precipitated cobalt species in the SiO₂ matrix. Samples containing cobalt nitrate and prepared with a molar ratio of H₂O/TEOS of 11.67 were studied as a function of annealing temperature. It was found that the added element has a remarkable influence on the final structure of this kind of samples and at relatively high temperatures the cobalt compounds react with the silica matrix forming a cobalt silicate.     

Synthesis,Crystal Structure and Thermal Decomposition of [HGdP2O7 · 2 H2O] · NH3 Electric properties of HGdP2O7 and Gd2P4O13

A new gadolinium diphosphate [HGdP₂O₇ · 2 H₂O] · NH₃ was synthesized via a soft chemistry route from evaporation of aqueous solution. It crystallizes in the space group Pī with Z = 2 and the following unit cell dimensions: a = 6.4609(2), b = 6.9810(2), c = 9.813(4) ?, α = 81.345(3), β = 80.547(3), γ = 88.430(3)°. IR spectroscopy confirmed the presence of P-OH group, and both ammonia and water molecule in the studied material.

The thermal decomposition of [HGdP₂O₇ · 2 H₂O] · NH₃, as investigated by Controlled Rate Thermal Analysis, took place in three stages between -23 and 600 °C leading to the anhydrous salt HGdP₂O₇. The calcination of the synthesized product at 850 °C in a static air furnace allowed us to obtain the tetraphosphate Gd₂P₄O₁₃. X-ray powder diffraction and infrared spectroscopy were used to identify these materials.

The electrical properties of HGdP₂O₇ and Gd₂P₄O₁₃ were investigated through impedance complex analysis. Modest conductivity has been observed in both materials at relatively medium temperature range. Activation energies of 0.62 and 1.21 eV, were deduced from the Arrhenius plots for HGdP₂O₇ and Gd₂P₄O₁₃, respectively.     

Nanocomposites Fe2O3/SiO2-Preparation by Sol-Gel Method and Physical Properties

Magnetic nanocomposites γ-Fe₂O₃/silica were prepared by a one-step sol-gel method. The sol was prepared by TEOS (tetraethyl orthosilicate) acid hydrolysis in the presence of an iron salt soluble in methanol. After gelation and drying, the transparent samples were characterized after treatment at different temperatures. The particle size, observed by HR TEM, was in the range of 2–10 nm and depended on Fe-concentration and heating temperature. Magnetic measurements showed either a ferromagnetic or a superparamagnetic behaviour and could be explained by the particle size. The dependence of the magnetic behaviour on the particle size was also studied by Mössbauer spectroscopy. The samples in which the Fe₂O₃ particle size was approximately 10 nm showed magnetic splitting (sextet) at room temperature, while smaller particles (2–3 nm) showed this splitting only at the temperature of liquid helium. The optomagnetic properties of the samples were also measured (Kerr effect).     

新型球形纳米空心SiO2的模板合成方法研究

以纳米碳酸钙颗粒为新颖的无机模板剂, 硅酸钠为无机硅源, 通过溶胶-凝胶法形成CaCO₃/SiO₂的核壳结构; 随后通过高温煅烧、酸溶和干燥处理, 合成出了具有高比表面积的球形纳米空心二氧化硅粒子. 然后, 分别采用TEM, SEM, EDS, XRD, FTIR和TG等测试手段对样品进行了分析和表征, 并考察了不同合成条件, 如反应温度、反应pH值、煅烧温度和包覆反应时SiO₂/CaCO₃的配比对纳米空心二氧化硅粒子的比表面积变化. 实验结果表明: 较高的反应温度如60～80 ℃, pH值9左右、SiO₂包覆量为碳酸钙质量的10%, 以及煅烧温度为700 ℃, 有利于形成空心形貌较好、比表面较大的球形纳米空心二氧化硅.     

Synthesis,Crystal Structure,and Characterization of A New Adduct Bis-(2-Amino-3-Benzyloxypyridinium) Selenate Monohydrate [C12H13N2O]2SeO4.H2O

Abstract

A new adduct bis-(2-amino-3-benzyloxypyridinium) selenate monohydrate, [C₁₂H₁₃N₂O]₂SeO₄.H₂O, has been synthesized by slow evaporation at room temperature using 2-amino-3-benzyloxypyridine as the structure-directing agent. The structure, determined by single-crystal X-ray diffraction at 298 K, can be described as organic-inorganic tunnels with different forms built by infinite inorganic chains parallel to the c axis and connected to the organic cations. In this atomic arrangement, hydrogen bonds and van der Waals interactions between the different species play an important role in the tri-dimensional network cohesion. Solid-state ¹³C and ⁷⁷Se MAS NMR spectroscopy results are in agreement with the X-ray structure.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional figures and tables.]     

新型球形纳米空心SiO2的模板合成方法研究

以纳米碳酸钙颗粒为新颖的无机模板剂,硅酸钠为无机硅源,通过溶胶-凝胶法形成CaCO3／SiO2的核壳结构;随后通过高温煅烧、酸溶和干燥处理,合成出了具有高比表面积的球形纳米空心二氧化硅粒子．然后,分别采用TEM,SEM,EDS,XRD,FTIR和TG等测试手段对样品进行了分析和表征,并考察了不同合成条件,如反应温度、反应pH值、煅烧温度和包覆反应时SiO2／CaCO3的配比对纳米空心二氧化硅粒子的比表面积变化．实验结果表明：较高的反应温度如60～80℃,pn值9左右、SiO2包覆量为碳酸钙质量的10％,以及煅烧温度为700℃,有利于形成空心形貌较好、比表面较大的球形纳米空心二氧化硅。     

Synthesis and Thermal Behavior of the Hydrogen Praseodymium Diphosphate (HPrP2O7·3H2O)

The preparation of a new acid lanthanide diphosphate is reported. The acid praseodymium diphosphate, obtained as a trihydrate salt, is investigated by chemical analysis, X-ray powder diffraction and IR spectroscopy. The study of the thermal behavior of HPrP₂O₇·3H₂O shows that its dehydration begins at 367 K. A scheme of its decomposition is proposed.This revised version was published online in November 2005 with corrections to the Cover Date.     

Preparation and characterization of Al/B/Fe2O3 nanothermites

A sol-gel synthetic approach combined with an ultrasonic method was utilized to prepare Al/B/Fe2O3 nanothermites.The structure and properties of the prepared nanothermites were characterized by thermogravimetric analysis,differential scanning calorimetry,scanning electron microscopy,X-ray diffraction,and an impact sensitivity test.The results verified that the nano-aluminum and the micro-boron were uniformly dispersed in the pores of the iron oxide gel.The heat of the prepared Al/B/Fe2O3 nanothermites was 1.3 times that of the simple physically mixed sample.In addition,the heat of the combustion test showed that these materials were indeed energetic.Small-scale safe experiments also showed that the prepared materials through sol-gel were relatively insensitive to standard impact.     

Hydrothermal Synthesis and Characterization Properties of C7H12N2[H2PO4]2.1/2H2O

An orthophosphoric hybrid material was successfully prepared by a hydrothermal reaction at 110 °C. A single crystal X-ray structure, thermal behavior, IR, and NMR spectroscopy investigations are given for a new organic cation bis dihydrogenomonophosphate C₇H₁₂N₂[H₂PO₄]₂.1/2H₂O. The latter has been synthesized hydrothermally using 2,4-diaminotoluene (DAT) and orthophosphoric acid. The atomic arrangement can be described as inorganic sheets alternating with inorganic-organic layers. The organic group C₇H₁₂N⁺ ₂ is located between inorganic groups to build multiple hydrogen bonds to ensure the three-dimensional cohesion network. The thermal behavior and IR, NMR and impedance spectroscopy studies are discussed for the powder samples of this compound.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Sol-Gel Fabrication and Properties of Silica Cores of Optical Fibers Doped with Yb3+, Er3+, Al2 O3 or TiO2

Optical cores of preforms for drawing optical fibers doped with Er3+ and Yb3+ were fabricated by the sol-gel method with the aim of increasing the thickness of glass layers coated in a single coating cycle and to determine the relation between the preparation conditions and optical properties of the fibers. Al2O3-P2O5-SiO2 and TiO2-P2O5-SiO2 glasses have been studied as matrices for entrapping the rare-earth elements. Input sols have been prepared from silicon and titanium alkoxides, AlCl3, ErCl3, YbCl3, POCl3, water and a modifier under acidic catalysis of HCl. The sols were coated on the inner wall of a silica substrate tube and the gel layers were sintered at high temperatures up to 2000°C after which the tube was collapsed into the preform. Continuous and homogenous glass films with the maximum thickness of about 8 m were fabricated. The influence of high-temperature heat treatment of the layers on their composition and optical attenuation was observed. The amplified stimulated emission of Er3+ around 1.55 m was measured under the excitation of the fibers by an Nd : YAG laser at 1.064 m.     

Synthesis and Structural Analysis of ϵ‐Fe2O3

Powder material of ?‐Fe₂O₃ was obtained by thermal decomposition of the clay mineral nontronite and subsequent isolation of the ferric oxide by leaching the silicate phases. Additionally, crystals of ?‐Fe₂O₃ were grown as precipitates by internal oxidation of a Pd₉₆Fe₄ alloy. Analysis of the precipitate crystals by electron diffraction yields an orthorhombic crystal system and space group Pna2₁ ab initio. X‐ray diffraction data of the powder containing small amounts of Al substituting Fe were refined by the Rietveld method. The refinement yields lattice parameters a = 507.15 pm, b = 873.59 pm and c = 941.78 pm, and atom positions. ?‐Fe₂O₃ is isostructural with κ‐Al₂O₃, AlFeO₃, and GaFeO₃ having an anion stacking sequence /ABAC/, and 1/4 of the cations in tetrahedral co‐ordination. Some strongly distorted FeO₆ octahedrons with one large Fe‐O distance, which may be considered as a 5+1 co‐ordination, appear to be characteristic for ?‐Fe₂O₃. The structure shows elements known from silicates and oxyhydroxides of iron, respectively.     

Thermal decomposition of hydronium jarosite (H3O)Fe3(SO4)2(OH)6

Thermogravimetry combined with mass spectrometry has been used to study the thermal decomposition of a synthetic hydronium jarosite. Five mass loss steps are observed at 262, 294, 385, 557 and 619°C. The mass loss step at 557°C is sharp and marks a sharp loss of sulphate as SO₃ from the hydronium jarosite. Mass spectrometry through evolved gases confirms the first three mass loss steps to dehydroxylation, the fourth to a mass loss of the hydrated proton and a sulphate and the final step to the loss of the remaining sulphate. Changes in the molecular structure of the hydronium jarosite were followed by infrared emission spectroscopy. This technique allows the infrared spectrum at the elevated temperatures to be obtained. Infrared emission spectroscopy confirms the dehydroxylation has taken place by 400 and the sulphate loss by 650°C. Jarosites are a group of minerals formed in evaporite deposits and form a component of the efflorescence. The minerals can function as cation and heavy metal collectors. Hydronium jarosite has the potential to act as a cation collector by the replacement of the proton with a heavy metal cation.     

Action of a Fluorescent Chemosensor for Cu2+ Encapsulated in Silica Xerogel

The fluorescent chemosensor of the type Ant-NH-O-O-NH-Ant for Cu²⁺ ions has been designed by means of a supramolecular approach, as follows: two anthracene (Ant) fragments as fluorophore subunits have been linked by a noncyclic NH-O-O-NH quadridentate ligand as a receptor. The interaction of Cu²⁺ - receptor is signalled through the enhancement of the anthracene fluorescence when the receptor, i.e., the dioxodiamine chain subunit of the sensor is able to stop a photoinduced electron-transfer mechanism. The experiments with the chemosensor encapsulated in silica xerogel by the sol-gel processing are described.     

溶胶-凝胶法制备镶嵌在SiO_2玻璃中的InAs纳米晶

以As2 O3,InCl3·4H2 O和正硅酸乙酯为原料 ,通过水解、缩聚制备了xIn2 O3-xAs2 O3- 10 0SiO2 (x =0 .5～ 7.5 )凝胶 .在氧气中加热到 45 0℃对凝胶热处理使其转化成凝胶玻璃 ,再在 2 0 0～ 5 0 0℃与氢气反应 ,结果在SiO2 凝胶玻璃中形成了立方相InAs.利用XRD测试了InAs纳米颗粒的大小 ,发现随着反应温度的升高及掺杂量的增加 ,InAs纳米颗粒粒径从 6增大到 2 9nm .电子衍射表明凝胶玻璃中的InAs纳米颗粒为多晶结构     

Crystal Structures of Na3PO2S2 · 11H2O and Na3POS3 · 11H2O

Summary.  Single crystals of sodium dithiophosphate undecahydrate (Na₃PO₂S₂ · 11H₂O) and sodium trithiophosphate undecahydrate (Na₃POS₃ · 11H₂O) were grown from aqueous solution. The crystal structures of Na₃PO₂S₂ · 11H₂O (P2₁2₁2₁; a = 1248.1(1), b = 945.2(1), c = 1383.1(1) pm; R ₁ = 0.0202, wR ₂ = 0.0502) and Na₃POS₃ · 11H₂O (Pna2₁; a = 1262.0(2), b = 947.6(2), c = 1431.5(2) pm; R ₁ = 0.0720, wR ₂ = 0.1371) are related to each other in a sense that all constituting units are arranged in similar positions and with similar orientations. The geometries of the anions were determined with high accuracy; thus, the structural parameters of the POS³⁻ ₃ anion were measured for the first time. Received September 25, 2001. Accepted January 21, 2002     

羧基化核壳磁性纳米Fe3O4吸附剂的制备及对Cu2+吸附性能

在以共沉淀法制备的磁性纳米Fe3O4粒子(Magnetic nanoparticles, MNP)表面进行了化学修饰, 制备了一种新型富含羧基功能团的核壳磁性纳米吸附剂(Carboxylic functionalized Fe3O4 magnetic nanoparticles, CMNP). 利用透射电子显微镜(TEM)、 X射线衍射仪(XRD)、 X射线能量色散谱(EDS)、 振动样品磁强计(VSM)、 傅里叶变换红外光谱(FIIR)和热重分析仪(TGA)对CMNP的形貌、 结构、 化学组成和磁性能进行了表征, 并考察了吸附剂对Cu2+的吸附性能, 研究了溶液pH值、 吸附时间和Cu2+初始浓度对吸附性能的影响. 结果表明, 羧基化核壳磁性纳米Fe3O4颗粒的平均粒径为15 nm, 具有良好的超顺磁性, 饱和磁化强度为41.84 A·m2/kg, 在10 min中内可达到吸附平衡, 在pH=7.0时吸附量最高, 吸附等温数据符合Langmuir模型, 饱和吸附量qm= 43.48 mg/g.