New Synthesis and Magnetic Properties of NiFe2O4/SiO2 and Co0.5Zn0.5Fe2O4/SiO2 Nanocomposites Using Tetraglycolatosilane as Precursor

In this work the new synthesis and magnetic properties of NiFe₂O₄/SiO₂ and Co_0.5Zn_0.5Fe₂O₄/SiO₂ nanocomposites using a water‐soluble silica precursor, tetraglycolatosilane (THEOS), by the sol‐gel method were reported. Nanocomposite were obtained by the thermal decomposition of the organic part at different annealing temperatures varying from 400 to 900 °C. Studies carried out using XRD, FT‐IR, TEM, STA (TG‐DTG‐DTA) and VSM techniques. XRD patterns show that NiFe₂O₄ and Co_0.5Zn_0.5Fe₂O₄ have been formed in an amorphous silica matrix at annealing temperatures above 600 and 400 °C, respectively. It is found that when the annealing temperature is up to 900 °C NiFe₂O₄/SiO₂ and Co_0.5Zn_0.5Fe₂O₄/SiO₂ samples show almost superparamagnetic behavior with a magnetization 4.66 emu/g and ferromagnetic behavior with a magnetization 10.11 emu/g, respectively. The magnetization and coercivity values of nanocomposites using THEOS were considerably less than previous reports using TEOS. THEOS as a silica matrix network provides an ideal nucleation environment to disperse ferrite nanoparticles and thus to confine them to aggregate and coarsen. By using THEOS over the currently used TEOS and TMOS, organic solvents are not needed due to the entire solubility of THEOS in water. Synthesized nanocomposites with adjustable particle sizes and controllable magnetic properties make the applicability of ferrites even more versatile.     

An improved sequential extraction method to determine element mobility in pyrite-bearing siliciclastic rocks

A sequential extraction method was developed for pyrite-bearing (FeS₂) siliciclastic rocks. The focus of this study was to enhance the procedure by an improved oxidation step to completely dissolve not only organic matter but also microcrystalline pyrite. In the first experiment, four oxidation procedures were compared for pure pyrite at extraction temperatures of 25°C and 85°C with hydrogen peroxide (H₂O₂) as the main oxidant. It was found that pyrite dissolution was most effective by using a mixture of H₂O₂, ammonium acetate (NH₄OAc) and nitric acid (HNO₃) at 25°C. This procedure dissolved >90% pyrite, and detected >75% using solute iron measurements. The difference between these two results was explained by reprecipitation of secondary iron minerals. The procedure worked best at 25°C, since solvent evaporation at 85°C amplified iron oversaturation and precipitation. For the pyrite-bearing siliciclastic rocks, two sequential extraction schemes were compared to optimise solid–solvent ratio, extraction step order and type of solvent. Eventually, the most effective step order identified for siliciclastic rocks containing pyrite and little organic matter was to first (1) remove the exchangeable fraction, followed by (2) dissolution with acid and afterwards (3) with a reducing agent. The (4) oxidation step was performed last.     

Organofunctional Silica Aerogels

Organically modified silica aerogels were prepared from mixtures of tetramethoxysilane (TMOS) and organofunctional alkoxysilanes RSi(OMe)₃ with R=mercaptopropyl, diphenylphosphinoethyl and chloropropyl. The base catalyzed hydrolysis and condensation reactions, followed by supercritical drying with liquid carbon dioxide were investigated. Starting from 9:1 mixtures of TMOS and RSi(OMe)₃, incorporation of the functional moieties succeeded quantitatively. Increasing the percentage of RSi(OMe)₃ to 20% or 40% leads to an incomplete condensation of the RSiO_1,5 units to the SiO₂ network. Compared with an unmodified silica aerogel, the microstructure of the resulting hybrid aerogels is nearly uninfluenced for the 9:1 mercapto-and chloro-modified samples, while in the phosphino-modified sample the typical pore radii distribution is disturbed by the bulky organic groups. The organofunctional aerogels decompose between 210 and 650°C.     

About the synthesis and thermal stability of SiO2-aerogel

Aerogels are extremely porous high-tech materials based on inorganic oxides, especially silica. The paper describes synthesis and properties of SiO₂-aerogel, and changes occurring during heating of SiO₂-aerogel in the temperature range from 20 to 1000°C. Four thermoanalytical methods were used: Thermodilatometry, Differential thermal analysis, Thermogravimetry and Derivative thermogravimetry.     

Nano particles of iron oxides in SiO<Subscript>2</Subscript> glass prepared by ion implantation

Quartz (SiO₂) glass was implanted with 5 × 10^{16 57}Fe ions/cm² at a substrate temperature of 500 °C, and annealed at temperatures between 700 and 950 °C. The implanted and annealed plates were characterized by conversion electron Mössbauer spectroscopy (CEMS), and measured by a Kerr effect magnetometer or a vibration sample magnetometer. Kerr effect measurement of as-implanted SiO₂ glass showed ferromagnetism at room temperature. CEM spectrum of the as-implanted glass consisted of magnetic relaxation peaks of finely dispersed metallic Fe species, and paramagnetic doublets of Fe³⁺ and Fe²⁺ species. The sample heated at 700 °C contained large grains of metallic Fe and a lot of oxidation products of Fe²⁺ species. After oxidation at temperatures higher than 800 °C, the samples showed also ferromagnetism, which was attributed mainly to ferromagnetic ε-Fe₂O₃ precipitated in SiO₂ matrix. Small amounts of α-Fe₂O₃ were produced at 950 °C. The results suggest that ion implantation and oxidation make a transparent ferromagnetic glass possible.     

Thermal study of naphthylammonium- and naphthylazonaphthylammonium-montmorillonite

The blue organo-clay color pigment (OCCP) naphthylazonaphthylammonium-montmorillonite was synthesized from the white naphthylammonium-montmorillonite by treating with NaNO₂, the azo colorant being located in the interlayer space. The following effects on the basal spacing of naphthylazonaphthylammonium-and naphthylammonium-clay were investigated: (1) the amount of naphthylammonium loading the clay, (2) the amount of NaNO₂ used for the staining, (3) aging of the preparation suspension and (4) thermal treatment. Samples were heated at 120, 180, 240, 300 and 360°C and diffracted by X-ray. During aging, some of the dye decomposed. Samples, after one day aging, were investigated by DTA. During the dehydration stage both organo-clays gradually decomposed, the naphthylammonium-clay at 120°C and the OCCP at 180°C. That fraction of organic matter, which did not escape, was air-oxidized at above 200°C and charcoal was obtained. The appearance and size of the DTA exothermic peaks depended on the amount of organic matter, which did not escape and this depended on the total amount of organic matter in the DTA cell. DTA proved that naphthylammonium reacted with NaNO₂ to form OCCP.     

Apparent low surface areas in microporous SiO2-xerogels

Nitrogen adsorption at −195°C serves as routine method for the measurement of surface area of porous materials derived by sol-gel procedures. In a systematic study of the simultaneous effect of the pH and water-silane ratio of the starting solutions of preparation of SiO₂ xerogels on their surface areas, it was found that conditions of high acidity and low water/silane ratio result in microporous materials, the surface of which cannot be accessed by N₂ at −195°C, within a realistic time scale, but only by CO₂ at 0°C. In a typical result for TMOS/water/methanol = 1/2/3 at pH=1.0, the apparent N₂-area was zero, while the CO₂-area was 414 m²/gr. It is recommended to recheck apparent N₂-low surface areas of sol-gel materials by CO₂ adsorption. The behavior of pyrene-doped xerogels of this type is in agreement with the structural characterization by adsorption.     

Thermal decomposition of the carbon nanotube/SiO<Subscript>2</Subscript>precursor powders

Summary TG-DSC-MS (thermogravimetry-differential scanning calorimetry-mass spectrometry) coupling techniques were used to make a simultaneous characterizing study for the thermal decomposition process of the carbon nanotube (CNT)/SiO₂precursor powders prepared by rapid sol-gel method. The thermal stability of the CNT and the SiO₂pure gel were investigated by TG-DSC. The results showed that the oxidation of CNT began from 530 and combusted at about 678°C at the heating rate of 10°C min^-1in air. Moreover, the faster the heating rate, the higher the temperature of CNT combustion. The appropriate calcinations temperature of the CNT/SiO₂precursor powders should be held for 1 h at 500°C.     

Study of thermal behaviour of organic matter from natural phosphates (Youssoufia - Morocco)

Thermogravimetry (TG), differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) were used to study the thermal behaviour of the organic matter in the natural phosphate and its concentrate kerogen from the Moroccan deposit. The TG analysis showed that both the investigated samples exhibited a one-step thermal oxidation in the main mass loss area, between 160 and 540°C, attributed to the hydrocarbon material. When DSC analyses of oxidation as well as pyrolysis yielded two evolutionary stages of the hydrocarbon in this temperature range : the first one at 160-360°C and the second one above 360°C. Pyrolytic kerogen decomposition was monitored by measuring changes in the principal FTIR organic bands. The results showed, in the first stage, the progressive decrease of signals due to CH₂ and CH₃ vibrations as well as the carbonyl and carboxylic bands, and their subsequent disappearance at 300°C. In the second stage above 400°C, the signal due to the aromatic components (1600 cm^-1) appeared but decreased with increasing temperature up to 540°C. This revised version was published online in August 2006 with corrections to the Cover Date.     

On the nature of the processes occurring in silver doped SiO<Subscript>2</Subscript> films under heat treatment

The processes taking place on air-heating of SiO₂−Ag⁺ films and xerogels produced from the SiO₂ sols of different pH (3.7 or 9.5) were investigated. Silver nanoparticles 10–40 nm in size tolerant to oxidation at temperatures above 600 °C were found to be formed in the systems whatever the pH value of the starting sol. SiO₂ crystallization giving the cristobalite phase in the temperature range from 500 to 800 °C was shown to proceed only in the films produced from the acidic sol, while in those formed from the alkali one SiO₂ remained amorphous. A mechanism by which the formation of Ag nanoparticles and the cristobalite phase occurs in the films at the oxidative conditions is suggested.     

High-temperature thermal analysis study of the reaction between magnesium oxide and silica

The reaction between SiO₂ and MgO at temperatures up to 1500°C was studied using thermal analysis, with X-ray diffraction being used to identify reaction products. The reaction is slow and results in the formation of Mg₂SiO₄ and MgSiO₃, with minor amounts of SiO₂·nH₂O and residual amounts of unreacted SiO₂ and MgO. Complete reaction of the starting materials to form Mg₂SiO₄ can only be achieved by maintaining the mixture at 1500°C for extended periods of time (>1 h).     

Low temperature synthesis of Co<Subscript>2</Subscript>SiO<Subscript>4</Subscript>/SiO<Subscript>2</Subscript> nanocomposite using a modified sol–gel method

The paper presents a study on the preparation of Co₂SiO₄/SiO₂ nanocomposites by a new modified sol–gel method. We have prepared gels starting from tetraethylorthosilicate (Si(OC₂H₅)₄), cobalt nitrate Co(NO₃)₂·6H₂O and some diols: ethylene glycol (C₂H₆O₂), 1,2propanediol (C₃H₈O₂) and 1,3propanediol (C₃H₈O₂), for a final composition: 30% CoO/70% SiO₂. During the heating of the gels at 140 °C, a redox reaction takes place between NO₃ ⁻ ions and diol with formation of some carboxylate anions. These carboxylate anions react with the Co(II) ions to form coordination compounds embedded in silica matrix, as evidenced by FT-IR spectrometry and thermal analysis. These Co(II) coordinative compounds thermally decompose in the range 250–300 °C to the corresponding oxides: CoO and/or Co₃O₄ inside the matrices pores. When CoO results, it reacts with SiO₂ at low temperature leading to Co₂SiO₄, which crystallizes at 700 °C. XRD patterns of the samples annealed at temperatures lower than 700 °C were characteristic to amorphous phases. The samples annealed at temperatures ≥700 °C, contain Co₂SiO₄ (olivine) as unique crystalline phase inside the amorphous silica matrix, according to XRD patterns. As evidenced by TEM images, Co₂SiO₄ nanoparticles are homogenously dispersed inside the silica matrix.     

Vanadium Nitride Films Formed by Rapid Thermal Processing (RTP): Depth Profiles and Interface Reactions Studied by Complementary Analytical Techniques

The nitridation of vanadium films in molecular nitrogen and ammonia using a RTP‐system was investigated. The V films were deposited on silicon substrates covered by 100 nm thermal SiO₂. For a few experiments sapphire substrates were used. Nitride formation at high temperatures (900 and 1100 °C) and interface reactions and diffusion of oxygen out of the SiO₂‐layer into the metal lattice at moderate temperatures (600 and 700 °C) were studied. For characterisation complementary analytical methods were used: X‐ray diffraction (XRD) for phase analysis, secondary neutral mass spectrometry (SNMS) and Rutherford Backscattering (RBS) for acquisition of depth profiles of V, N, O, C and Si, transmission electron microscopy (TEM) in combination with electron energy filtering for imaging element distributions (EFTEM) and recording electron energy loss spectra (EELS) to obtain detailed information about the initial stages of nitride, oxide and oxynitride formation, respectively, and the microstructure and element distributions of the films. In these experiments the SiO₂‐layer acts as diffusion barrier for nitrogen and source for oxygen causing the formation of substoichiometric vanadium oxides and oxynitrides near the V/SiO₂‐interface primarily at temperatures ≤ 900 °C. At a temperature of 1100 °C just a small amount of oxynitride forms near the interface because rapid diffusion of nitrogen and fast formation of VN (diffusion barrier for oxygen) inhibit the outdiffusion of oxygen into the metal layer. In the 600 °C regime, in argon atmosphere oxynitride phases observed in the surface region of these films originate from reaction of residual oxygen in the argon gas, whereas NH₃ as process gas does not lead to oxide or oxynitride formation at the surface (apart from the oxidation caused by storage). NH₃ seems to support the diffusion of oxygen out of the SiO₂‐layer. During the decomposition of ammonia at higher temperatures hydrogen is formed, which could attack the SiO₂. In contrast, sapphire substrates do not act as oxygen source in the 600 °C regime and change the nitridation behaviour of the vanadium films.     

SiO2/SnO2 and Sn/Sb-oxide/SiO2 gel-derived composites. Part 2: Thermal evolution and phase analysis

The thermal behaviour of samples with nominal composition 80/20=SiO₂/SnO₂, class B, 76.8/19.2/4.0=SiO₂/SnO₂/Sb₂O₅, class C₁, and 76.8/19.2/2.0/2.0=SiO₂/SnO₂/Sb₂O₅/Sb₂O₃, class C₂, is studied in the interval 25–1050°C by various instrumental methods. Results on these classes of samples, obtained from alkoxide precursors, are compared themselves and with samples of class A obtained from Si(OEt)₄ and SnCl₄. The segregation and crystallization of SnO₂ occurs at 400°C in the presence of microdomains of SnO₂·nH₂O in the SiO₂ gel matrix (class A), whereas it is observed at 700°C for samples B and C composed of Sn and Sb cations homogeneously dispersed in SiO₂. This fact implies different mechanisms of SnO₂ nucleation and growth. The crystallization of SiO₂ is observed at 1200°C for samples A, at 1050°C for B and at 800°C for C. For this latter, the presence of Sb-oxide/ SiO₂ reactive glass is invoked to the low-temperature crystallization of SiO₂. G. Carturan, R. Ceccato, R. Campostrini, G. Principi, and U. Russo, submitted to J. Sol-Gel Sci. Tech.     

Hydrodeoxygenation of Furfural over Unsupported,SiO2-supported or Metal-promoted Mo Carbides: Tunning the Selectivity between 2-Methylfuran and C10 Furoins Diesel Precursors

The hydrodeoxygenation of furfural (FF) over Mo carbides in liquid phase at 200 °C, 30 bar of H₂ for 4 h in 2-butanol was investigated. Unsupported and SiO₂-supported Mo carbide with different crystallographic phases (β-Mo₂C/SiO₂ and α-MoC/SiO₂), and in the presence of Cu and Ni as promoters were studied. The reactivation treatment under H₂ atmosphere of the passivated Mo carbides was investigated by XAS. The results show that Mo is present in different states of oxidation in the passivated catalysts, with more severe oxidation in the bimetallic systems, in which the original carbides are not restored after reactivation. Finally, the product distribution in the HDO of furfural is modified as a function of catalyst oxidation degree. Using the less oxidized Mo carbide (β-Mo₂C), a higher yield to 2-methylfuran is obtained, while C₁₀ condensation products are formed for the more oxidized catalysts.     

Direct catalytic oxidation of methane to formaldehyde: New investigation opportunities provided by an improved flow circulation method

An improved flow circulation reactor with reaction mixture quenching was used to study the direct oxidation of methane to formaldehyde at 600–770°C, a CH₄/O₂ volume ratio of 1: 1 in the starting mixture, and gas mixture flow rates of 0.4–2.0 l/h. It was found that, in the presence of a surface containing SiO₂ (quartz reactor walls, the surface of silica packing materials, or the surface of SiO₂ as a catalyst constituent), the process occurred by a heterogeneous-homogeneous mechanism with chain continuation in the volume of a gas phase. The process was controlled by the size and shape of the free reaction volume, the contact surface area, and the residence time of a mixture in the reaction volume. The introduction of typical oxidation catalysts containing, for example, Pt or V₂O₅ as an active component along with SiO₂ resulted in a decrease in the yield of and selectivity for formaldehyde.     

An effect of heat processing on catalytic activity of a system MnO x ,SiO2/TiO2/Ti

An effect of annealing in air at temperatures 250, 350, 500, and 700°C on composition, surface structure, and catalytic activity in CO oxidation of a system MnO _x ,SiO₂/TiO₂/Ti formed by combining methods of plasma electrolytic oxidation and impregnation was examined.     

Struktur und katalytische Eigenschaften von Molybdänoxid-Trägerkatalysatoren bei einigen Oxydationsreaktionen

Structure and Catalytic Properties of Molybdenum Oxide Supported Catalysts in Some Oxidation Reactions Molybdenum supported catalysts were prepared by using different precursor compounds such as Mo(π-C₃H₅)₄, [Mo(OC₂H₅)₅]₂, MoCl₅, (NH₄)₆Mo₇O₂₄, and their catalytic behaviour in some oxidation reactions was studied. During the preparation process, as a result of interaction between the molybdenum compound used and the support, different surface compounds with strongly differing catalytic properties have been formed. MoO₃ and supported catalysts with MoO₃ crystallites on the surface, catalyse the H₂ oxidation at temperatures above 400°C and the CO oxidation at temperatures of about 500°C. The reaction proceeds according to a redox mechanism. On surface compounds of molybdenum which exist on the surface if organic complexes are used as precursors, the catalytic H₂ oxidation occurs even at 100°C with a high reaction rate. The catalytic CO oxidation on these catalysts occurs at temperatures of about 300°C. An associative mechanism on coordinative unsaturated Mo^VI sites is discussed.     

Highly efficient and green oxidation of alkanes and alkylaromatics with hydrogen peroxide catalysed by silver and vanadyl on mesoporous silica‐coated magnetite

A heterogeneous catalyst (FeSi/Ag/VO) based on silver and vanadyl as active sites and mesoporous silica‐coated nanospheres of magnetite (Fe₃O₄@m‐SiO₂) as support was successfully prepared by deposition of Ag nanoparticles and the covalent grafting of vanadyl(IV) acetylacetonate on Fe₃O₄@m‐SiO₂. The catalyst exhibited excellent activity for the oxidation of alkanes, benzene and alkylaromatics using green oxidant H₂O₂ and oxalic acid in acetonitrile at 60 °C.     

High-temperature oxidation of FeCrAl alloy with alumina–silica–ceria coatings deposited by sol–gel method

One-layer protective coatings made up of SiO₂–Al₂O₃ or SiO₂–Al₂O₃–CeO₂ oxides were synthesized on a FeCrAl alloy substrate by the sol–gel method from sols containing tetraethyl orthosilicate, aluminum tri-sec-butoxide and cerium(III) 2,4-pentanedionate as the precursors. Coating solutions with the Si:Al:Ce molar ratio of 3:1:0, 3:1:0.1; 3:1:0.01, and 3:1:0.001 were used. The composition and morphology of the obtained gels were examined by TG/DSC, XRD, and SEM techniques. It was found that a small addition of cerium affected the morphology of the forming coatings and improved the FeCrAl alloy resistance to high-temperature oxidation (in air at T = 900 °C for t = 100 h). The oxidation of all the investigated samples conformed to the parabolic rate. The protection effectiveness of the one-layer coatings after 100 h of high-temperature oxidation was as high as 70 %.