V2O5/TiO2 Catalytic Xerogels Raman and EPR Studies

Raman spectroscopy and Electron Paramagnetic Resonance (EPR) studies were performed on a series of V₂O₅/TiO₂ catalysts prepared by a modified sol-gel method in order to identify the vanadium species. Two species of surface vanadium were identified by Raman measurements, monomeric vanadyls and polymeric vanadates. Monomeric vanadyls are characterized by a narrow Raman band at 1030 cm^–1 and polymeric vanadates by two broad bands in the region from 900 to 960 cm^–1 and 770 to 850 cm^–1. The Raman spectra do not exhibit characteristic peaks of crystalline V₂O₅. These results are in agreement with those of X-ray Diffractometry (XRD) and Fourier Transform Infrared (FT-IR) previously reported (C.B. Rodella et al., J. Sol-Gel Sci. Techn., submitted). At least three families of V⁴⁺ ions were identified by EPR investigations. The analysis of the EPR spectra suggests that isolated V⁴⁺ ions are located in sites with octahedral symmetry substituting for Ti⁴⁺ ions in the rutile structure. Magnetically interacting V⁴⁺ ions are also present as pairs or clusters giving rise to a broad and structureless EPR line. At higher concentration of V₂O₅, a partial oxidation of V⁴⁺ to V⁵⁺ is apparent from the EPR results.     

Investigation of surface structure and composition of in situ annealed Fe–Mn binary alloy samples using RHEED and electron spectroscopy

The formation of oxides at the surface of Fe–1.5%Mn and Fe–0.6%Mn binary alloys was investigated as a function of the conditions of the heat treatments. Both the influence of temperature and the atmosphere under which the experiments were performed were studied. The range of annealing temperatures was adjusted to 800°C. The atmosphere consisted of a mixture of N₂–5%H₂ and traces of water vapour, with different fixed dew points ranging from −10°C to −30°C. The state of the annealed surfaces was determined using in situ analytical devices attached to the annealing reactor in order to avoid surface contamination or the formation of native oxides after the experiments due to contact with air. The structure and composition of the surfaces were determined by reflection high-energy electron diffraction (RHEED) and electron spectroscopy (XPS, AES). Copyright © 2002 John Wiley & Sons, Ltd.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. 58. Zur Kenntnis von 2-(Dimethylaminomethyl)ferrocenyl-Verbindungen des Vanadiums,Molybdäns,Wolframs, Thoriums und Urans

Contributions to the Chemistry of Transition Metal Alkyl Compounds. 58 On 2-(Dimethylaminomethyl)ferrocenyl Compounds of Vanadium, Molybdenum, Tungsten, Thorium, and Uranium Earlier results according to which dimethylaminomethylferrocenyl groups (FcN) are able to form stable organometallic chelate compounds were confirmed by synthesis of the heterobimetallic chelate compounds (FcN)₂VO · Li(acac) II , (FcN)MoO₂(acac) III , (FcN)WOCl₃ IV , (FcN)Th(acac)₃ V , and (FcN)UO₂(acac) VI from the corresponding metal acetylacetonates or oxidchlorides and (FcN)Li I . The new compounds were characterized by elemental analysis, the i.r., ¹H-n.m.r., and electron spectra and by their effective magnetic moments.     

Quantitative determination of sotolon, maltol and free furaneol in wine by solid-phase extraction and gas chromatography-ion-trap mass spectrometry

A method for the analytical determination of sotolon [4,5-dimethyl-3-hydroxy-2(5H)-furanone], maltol [3-hydroxy-2-methyl-4H-pyran-4-one] and free furaneol [2,5-dimethyl-4-hydroxy-3(2H)-furanone] in wine has been developed. The analytes are extracted from 50 ml of wine in a solid-phase extraction cartridge filled with 800 mg of LiChrolut EN resins. Interferences are removed with 15 ml of a pentane-dichloromethane (20:1) solution, and analytes are recovered with 6 ml of dichloromethane. The extract is concentrated up to 0.1 ml and analyzed by GC-ion trap MS. Maltol and sotolon were determined by selected ion storage of ions in the m/z ranges 120-153 and 79-95, using the ions m/z 126 and 83 for quantitation, respectively. Furaneol was determined by non-resonant fragmentation of the m/z 128 mother ion and subsequent analysis of the m/z 81 ion. The detection limits of the method are in all cases between 0.5 and 1 microg l(-1), well below the olfactory thresholds of the compounds. The precision of the method is in the 4-5% range for levels in wine around 20 microg l(-1). Linearity holds at least up to 400 microg l(-1), and is satisfactory in all cases. The recoveries of maltol and sotolon are constant (70 and 64%, respectively) and do not depend on the type of wine. On the contrary, in the case of furaneol, red wines show constant and high recoveries (97%), while the recoveries on white wines range between 30 and 80%. Different experiments showed that this behavior is probably due to the existence of complexes formed between furaneol and sulphur dioxide or catechols. Sensory experiments confirmed that the complexed forms found in white wines are not perceived by orthonasal olfaction, and that the furaneol determined by the method can be considered as the free and odor-active fraction.     

二氧化钒和三氧化二钒研究进展

VO₂和V₂O₃是优异的光、电、磁热敏材料，在多种技术领域中具有广阔的应用前景，已成为国内外新颖功能材料研究的热点之一。本文综述了VO₂和V₂O₃的粉体、陶瓷和薄膜的研究进展，并对相关问题进行讨论。     

Ionic liquid–modified cellulosic hydrogels for loading and sustained release of selenourea: an ensuing inhibition of tyrosinase activity

Cellulose-based hydrogel materials were prepared and modified with tannic acid and l-methionine using ionic liquid as the solvent. The gels were prepared to develop a sustained release medium for selenourea (SeU). The drug delivery characteristics of selenourea-loaded cellulose (CSeU), selenourea-loaded tannic acid-modified cellulose (CTSeU), and selenourea-loaded L-methionine-modified cellulose (CMSeU) were investigated in aqueous media and simulated gastric fluid (SGF) media. This modified gel beads have been characterized using field emission scanning electron microscope, X-ray energy-dispersive spectroscopy, Fourier transform infrared spectroscopy, thermogravimetry–differential thermal analysis and swelling properties and compared with those of the unmodified ones. We also investigated the inhibitory effects of SeU released from these gels on the activity of mushroom tyrosinase. Out of all the gel materials, CTSeU showed maximum SeU release both in water and SGF media. However, tyrosinase inhibitory action in PBS medium was comparable for all the three gel materials.     

Robust interface on ENR-50/TiO2 nanohybrid material based sol-gel technique: Insights into synthesis,characterization and applications in optical

In this work, the sol–gel technique was used to prepare a new organic–inorganic hybrid from Epoxidized Natural Rubber (ENR-50) and Titanium dioxide (TiO₂) by blending different content of titania precursors (10, 30, and 50 wt%) with an ENR-50 matrix. A wide range of analyses was conducted to understand the nature of this hybrid and also to evaluate its potential uses in applications required high refractive index such as micro optical and optoelectronic devices. Results indicated that the ring-opening reaction of epoxide groups in ENR-50 increased with the increase of titania content in the hybrid resulting a strong bonding between titania and ENR-50 through TiOC bond, which was observed in FTIR spectrum at 1027–1028 cm⁻¹. It is also observed a slight decrease in the intensity of the amorphous peak along with a new crystalline peak appeared at 2θ = 23 and 27° due to the crystalline nature of titania. The hybrids showed three thermal degradation steps in the range of temperature 76 to 769 °C due to the existence of the Ti moieties with the mixture of polymer chains, which in turn shifted the T_g at 24.3, 26.9 and 28.1 °C for the hybrid at 10, 30, and 50 wt% TiO₂ compared to the T_g of ENR-50 at −18.4 °C respectively. The morphology of the ENR-50 showed clear changes during of the synthesis of ENR-50/TiO₂ hybrids, these changes were proven by SEM, TEM, and AFM analyses. Uv–Vis results showed that the higher wavelength peak at 293 nm has shifted to 296, 298 and 300 nm for the hybrid at 10, 30, and 50 wt% TiO₂ respectively due to the strong interaction between titania precursors and ENR-50 matrix. Furthermore, the hybrids showed good optical transparency in the visible light range.     

Electrochemical properties and state of paramagnetic centers in copper-modified complex vanadium and titanium oxides

Complex vanadium and titanium oxides modified by copper ions are studied by the electrochemical and ESR methods. Oxides Cu _x V_2?y Ti _y O_5?δ·nH₂O (0<y<1.33) have a layered structure and oxides Cu _x Ti_1?y V _y O_5+δ·nH₂O (0<y<0.25), an anatase structure. The intercalation of cations Cu²⁺ into the hydrates leads to oxidation of V⁴⁺. According to ESR data, V⁴⁺ exists in the oxides in the form of VO²⁺ and an octahedral surround of oxygen (V⁴⁺?O₆), respectively. The electroreduction of ions of d-elements and chemisorbed oxygen in the oxides is analyzed. The intercalation of cations Cu²⁺ alters the content of V⁴⁺ and the chemisorption ability of the oxides. Possible reasons for this phenomenon are discussed.     

制备纳米V2O5的新方法及其电化学性能的研究

目前对锂离子电池正极材料的研究主要为达到如下目标而进行:高的比容量和能量密度,良好的循环性和寿命,资源丰富、价格便宜以及环境友好。已进行了广泛研究的LiCoO_2、LiNiO_2、LiMn_2O_4等锂离子电池正极材料,虽然具有较高的电压平台、良好的稳定性和寿命,但其容量相对较低和价格较高限制了其进一步的应用和发展。