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1.
The photoluminescence properties of xZnO–(100−x)SiO2 (x = 0, 5, 10, 20) containing 1% Eu2O3 prepared by a sol–gel method were systematically investigated. The results indicated that the relative proportion of f–f transitions to charge transfer (CT) absorption decreased with the increase of ZnO concentration. The intensity of 5D07FJ transitions of Eu3+ ions was enhanced with the increase of ZnO content due to local structure changes and decreased quantities of Eu3+ ions clusters. The results of fluorescence line narrow (FLN) spectra indicated that Eu3+ ions occupied one site in SiO2 glass and two sites in ZnO–SiO2 glasses. The second-order crystal field parameters were calculated. B20 and B22 for site 1 increased with excitation energy, while ones hardly changed for site 2.  相似文献   

2.
This article presents the results of our investigation on the obtaining of Ni0.65Zn0.35Fe2O4 ferrite nanoparticles embedded in a SiO2 matrix using a modified sol–gel synthesis method, starting from tetraethylorthosilicate (TEOS), metal (FeIII,NiII,ZnII) nitrates and ethylene glycol (EG). This method consists in the formation of carboxylate type complexes, inside the silica matrix, used as forerunners for the ferrite/silica nanocomposites. We prepared gels with different compositions, in order to obtain, through a suitable thermal treatment, the nanocomposites (Ni0.65Zn0.35Fe2O4)x–(SiO2)100–x (where x=10, 20, 30, 40, 50, 60 mass%). The synthesized gels were studied by differential thermal analysis (DTA), thermogravimetry (TG) and FTIR spectroscopy. The formation of Ni–Zn ferrite in the silica matrix and the behavior in an external magnetic field were studied by X-ray diffraction (XRD) and quasi-static magnetic measurements (50 Hz).  相似文献   

3.
Solid solution phases of a formula Fe8V10W16–xMoxO85 where 0≤x≤4, have been obtained, possessing a structure of the compound Fe8V10W16O85. It was found on the base of XRD and DTA investigations that these solution phases melted incongruently, with increasing the value of x, in the temperature range from 1108 (x=0) to 1083 K (x=4) depositing Fe2WO6 and WO3. The increase of the Mo6+ ions content in the crystal lattice of Fe8V10W16O85 causes the lattice parameters a=b contraction with cbeing almost constant. IR spectra of the Fe8V10W16–xMoxO85 solid solution phases have been recorded.  相似文献   

4.
Large-scale Li1+x V3O8 nanobelts were successfully fabricated using filter paper as deposition substrate through a simple surface sol–gel method. The nanobelts were as long as tens of micrometers with widths of 0.4–1.0 μm and thickness of 50–100 nm. The nanobelts were characterized by X-ray diffration (XRD), Fourier infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM). The formation mechanism of the nanobelts was investigated, showing that the morphology of the nanobelts is mainly determined by the calcination temperature. Electrochemical properties of the Li1+x V3O8 nanobelts were characterized by charge–discharge experiments, and the results demonstrate that the Li1+x V3O8 nanobelts exhibit a high discharge capacity (278 mAh g−1) and excellent cycling stability.  相似文献   

5.
The adsorption of reactant mixtures is quantitatively and qualitatively different from the adsorption of the individual reactants. Thus, O2 is almost not adsorbed on ZrO2; however, a considerable concentration of molecular oxygen was detected among the products of desorption after the adsorption of a mixture of NO + O2 and the total amount of desorbed molecules was greater by a factor of 10 than their total amount after the individual adsorption of NO and O2. Among the qualitative differences is the formation of the O2- radical anion on the surface only upon the adsorption of the mixture of NO + O2. Similarly, the number of desorbed molecules upon the simultaneous adsorption of C3H6, NO, and O2 was much greater than that upon their individual adsorption; this is related to the formation of paramagnetic and nonparamagnetic NO2–hydrocarbon complexes on the surface, which contained the NO2 group and a hydrocarbon fragment.  相似文献   

6.
This work reports the study of Bi4V2–xBaxO11–1.5x (0.02≤x≤0.50) series, which is a potential source of solid electrolytes to apply in oxygen sensors. X-ray powder diffraction was used to point out the formation of major ionic conductive phases and minor ones. The modifications of vanadate substructure were probed, at short range, by Fourier-transform infrared spectroscopy. Differential scanning calorimetry evidenced the formation of tetragonal γ phase, which can be ionic conductive, for x=0.14.  相似文献   

7.
LiMn2O4-based spinels are of great interest as positive electrode materials for lithium ion batteries. LiCo x Mn2−x O4 (x = 0.0, 0.1, 0.2, 0.3, and 0.4) spinel phases have been synthesized by novel citric acid-modified microwave-assisted sol–gel method. The structural properties of the synthesized products have been investigated by X-ray powder diffraction and scanning electron microscopy. To improve the recharge capacity of Li/LiCo x Mn2−x O4 cells, the electrochemical features of LiCo x Mn2−x O4 compounds have been evaluated as positive electrode materials. The structural properties of Co-doped oxides are very similar to LiMn2O4 electrode. Techniques like cyclic voltammetry, charge–discharge and cycle life are also used to characterize the LiCo x Mn2−x O4 (x = 0.0, 0.1, 0.2, 0.3, and 0.4) electrodes.  相似文献   

8.
YBaCo4O7 compound is capable to intake and release a large amount of oxygen in the temperature range of 200–400°C. In the present study, the effect of Zn, Ga and Fe substitution for Co on the oxygen adsorption/desorption properties of YBaCo4O7 were investigated by thermogravimetry (TG) method. Due to fixed oxidation state of Zn2+ ions, the substitution of Zn2+ for Co2+ suppresses the oxygen adsorption of YBaCo4−xZnxO7. The substitution of Ga3+ for Co3+ also decreases the oxygen absorption capacity of YBaCo4−xGaxO7. This can be explained by the strong affinity of Ga3+ ions towards the GaO4 tetrahedron. Compared with Zn- and Ga-substituted samples, the drop of oxygen adsorption capacity is smallest for Fe-substituted samples because of the similar changeability of oxidation states of Co and Fe ions.  相似文献   

9.
Phase relations in the Zn2V2O7-Cu2V2O7 system were studied by high-temperature X-ray diffraction and differential thermal analysis. The major phase constituents of the system are solid solutions based on Zn2V2O7 and Cu2V2O7 polymorphs and their coexistence regions. The generation of α-Zn2 − 2x Cu2x V2O7 solid solution, where 0 ≤ x ≤ 0.30, leaves almost unchanged the stabilization temperature of the high-temperature zinc pyrovanadate phase. The α-Cu2 − 2x Zn2x V2O7 homogeneity range is 5 mol % Zn2V2O7. In the range 0.050 ≤ x ≤ 0.09 from 20 to ∼ 620°C, there is the two-phase field of α-Cu2V2O7 and β-Cu2V2O7 base solid solutions. At still higher temperatures, β-Zn2 − 2x Cu2x V2O7 and α-Cu2 − 2x Zn2x V2O7 coexist in the mixed-phase region. β-Zn2 − 2x Cu2x V2O7 solid solution, where 0 ≤ x ≤ 0.30, exists above 610 ± 5°C. The extent of the β′-Cu2V2O7-base solid solution is 9 to 65 mol % Zn2V2O7 at 615 ± 5°C, expanding to 0 mol % Zn2V2O7 with rising temperature. Original Russian Text ¢ T.I. Krasnenko, M.V. Rotermel’, S.A. Petrova, R.G. Zakharov, O.V. Sivtsova, A.N. Chvanova, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 10, pp. 1755–1762.  相似文献   

10.
Electrical conductivity in the monoclinic Li2TiO3, cubic Li1.33Ti1.67O4, and in their mixture has been studied by impedance spectroscopy in the temperature range 20–730 °C. Li2TiO3 shows low lithium ion conductivity, σ300≈10–6 S/cm at 300 °C, whereas Li1.33Ti1.67O4 has 3×10–8 at 20 °C and 3×10–4 S/cm at 300 °C. Structural properties are used to discuss the observed conductivity features. The conductivity dependences on temperature in the coordinates of 1000/T versus logeT) are not linear, as the conductivity mechanism changes. Extrinsic and intrinsic conductivity regions are observed. The change in the conductivity mechanism in Li2TiO3 at around 500–600 °C is observed and considered as an effect of the first-order phase transition, not reported before. Formation of solid solutions of Li2– x Ti1+ x O3 above 900 °C significantly increases the conductivity. Irradiation by high-energy (5 MeV) electrons causes defects and the conductivity in Li2TiO3 increases exponentially. A dose of 144 MGy yields an increase in conductivity of about 100 times at room temperature. Electronic Publication  相似文献   

11.
The efficiency of TiO2 (Degussa P-25) modified with an alkaline admixture (urea, BaO), sulfuric acid, or platinum in the photocatalytic oxidation of NO (50 ppm) with a flowing 7% O2 + N2 mixture under UV irradiation in a flow reactor at room temperature and atmospheric pressure is reported. Because of the progressive blocking of active sites of the photocatalyst by the reaction products (NO2, NO3), it is impossible to realize prolonged continuous removal of NO x (NO + NO2) from air without catalyst regeneration at elevated temperatures. The efficiency of the photocatalysts is characterized by specific photoadsorption capacity (SPC) calculated from the total amount of NO x adsorbed during 2-h-long irradiation. Modification of TiO2 with 5% BaO or 5% urea raises the SPC of the catalyst by a factor of 2–3. Presumably, this promoting effect is due to the basic properties of these dopants, which readily sorb NO2 and NO3. A considerable favorable effect on SPC is also attained by adding 0.5% Pt to (5% BaO)/TiO2. The SPC of the (0.5% Pt)/TiO2 catalyst depends on the state of the platinum. The samples calcined in air at 500°C, which contain Pt+ and Pt2+, have an approximately 2 times higher SPC than unpromoted TiO2 and ensure a much larger NO2/NO ratio at the reactor outlet. Conversely, the samples reduced in an H2 atmosphere at 200°C, whose platinum is in the Pt0 state, show a lower SPC than the initial TiO2 and cause no significant change in the NO2/NO ratio.  相似文献   

12.
Solid-phase interactions in the V2O5-Ta2O5-MoO3 system were studied. The formation of com- pounds TaVO5 and VTa9O25 in the V2O5-Ta2O5 binary system was verified. Tetragonal VTa9O25-base solid solutions of the general formula Ta5 + 4x V5 − 4x O25 (x = 0.25–1) and TaVO5-base solid solutions of the general formula Ta x Mo1 − x V2 − x O8 − 3x (x = 0.625–1) were found to form. Subsolidus phase equilibria in the V2O5-Ta2O5-MoO3 were determined.  相似文献   

13.
Platinum catalysts supported on indium-doped alumina were prepared by the sol–gel method. The method allows the incorporation of In3+ in the alumina network. The indium-doped alumina supports showed narrow pore size distribution (5.4–4.0 nm) and high specific surface areas (258–280 m2/g). The 27Al NMR-MAS spectroscopy identified aluminum in tetrahedral, pentahedral, and octahedral coordination; however, the intensity of the signal assigned to aluminum in pentahedral coordination diminishes with the increase of the content of indium. Total acidity determined by ammonia thermodesorption diminishes strongly in Pt/In–Al2O3 catalysts, suggesting a selective deposit of platinum over the acid sites of the support. The effect of the support in the platinum catalytic activity was evaluated in the n-heptane dehydrocyclization reaction. The selectivity patterns for such reaction were modified substantially in the doped Pt/In–Al2O3 catalysts, in comparison with the Pt-In/Al2O3–I coimpregnated reference catalyst. As an important result, the formation of benzene was suppressed totally over the indium-doped alumina sol–gel supports with a high content (3 wt%) of indium.  相似文献   

14.
Toward achieving selective catalytic reduction of NO x by hydrocarbons at low temperatures (especially lower than 200 °C), C2H2 selective reduction of NO x was explored on H-mordenite (H-MOR) catalysts in dielectric barrier discharge (DBD) plasma. This work reported significant synergistic effects of DBD plasmas and H-MOR catalysts for C2H2 selective reduction of NO x at low temperatures (100–200 °C ) and across a wide range of O2 content (0–15%). At 100 °C, NO x conversions were 3.3, 11.6 and 66.7% for the plasma alone, catalyst alone and in-plasma catalysis (IPC) cases (with a reactant gas mixture of 500 ppm NO, 500 ppm C2H2, 10% O2 in N2, GHSV = 12,000 h−1 and input energy density of 125 J L 1), respectively. At 200 °C, NO x conversions were 3.8, 54.0 and 91.4% for the above three cases, respectively. Also, strong signals of hydrogen cyanide (HCN) byproduct were observed in the catalyst alone system by an on-line mass spectrometer. By contrast, almost no HCN was detected in the IPC system.  相似文献   

15.
It was established by X-ray diffraction, TPR, and EPR that microemulsion (m.e.) synthesis yields the binary oxides ZrO2(m.e.) and CeO2(m.e.) and the mixed oxide Zr0.5Ce0.5O2(m.e.) in the form of a tetragonal, cubic, and pseudocubic phase, respectively, having crystallite sizes of 5–6 nm. The bond energy of surface oxygen in the (m.e.) samples is lower than in their analogues prepared by pyrolysis. Hydrogen oxidation on the oxides under study occurs at higher temperatures than CO oxidation. ZrO2(m.e.) and CeO2(m.e.) are active in O2 formation during NO + O2 adsorption, while CeO2 is active during CO + O2 adsorption, too. However, its amount here is one-half to one-third its amount in the pyrolysis-prepared samples, signifying a reduced number of active sites, which are Zr4+ and Ce4+ coordinatively unsaturated cations and Me4+-O2− pairs. O2 radical anions are stabilized in the coordination sphere of Zr4+ coordinatively unsaturated cations via ionic bonding, and in the sphere of Ce4+ cations, via covalent bonding. Ionic bonds are stronger than ionic-covalent bonds and do not depend on the ZrO2 phase composition. Zr0.5Ce0.5O2 is inactive in these reactions because of the strong interaction of Zr and Ce cations. It is suggested that Ce(4 + β)+ coordinatively unsaturated cations exist on its surface, and their acid strength is lower than that of Zr4+ and Ce4+ cations in ZrO2 and CeO2, according to the order ZrO2 > CeO2 ≥ Zr0.5Ce0.5O2. Neither TPR nor adsorption of probe molecules revealed Zr cations on the surface of the mixed oxide.  相似文献   

16.
 Nucleophilic vinylic substitutions of 4H-pyran-4-one and 2-methyl-4H-pyran-4-one with ammonia were calculated by the B3LYP method using the 6-31G(d,p) basis set. Bulk solvent effects of aqueous solution were estimated by the polarized continuum and Poisson–Boltzmann self-consistent reaction field models using the 6-311+G(d,p) basis set. In the gas phase different mechanisms were found for the two reaction systems calculated. The reaction of 4H-pyran-4-one proceeds through enol, whereas a feasible path for the less reactive 2-methyl-4H-pyran-4-one is the mechanism through a keto intermediate. Addition of ammonia in concert with proton transfer is the rate-determining step ofthe reaction. The mechanism proceeding either by a bimolecular nucleophilic substitution (SN2) or by one involving a tetrahedral zwitterionic intermediate is shown to be unlikely in the gas phase or nonpolar solution. The effects of bulk solvent not only consist in a reduction of the various activation barriers by about 25–40 kJ mol−1 but also in a change in the reaction mechanism. Received 26 May 2002 / Accepted 26 July 2002 / Published online: 14 February 2003  相似文献   

17.
The adsorption and activation of NO molecules on Cu-ZSM-5 catalysts with different Cu/Al and Si/Al ratios (from 0.05 to 1.4 and from 17 to 45, respectively) subjected to different pretreatment was studied by ultraviolet-visible diffuse reflectance (UV-Vis DR). It was found that the amount of chemisorbed NO and the catalyst activity in NO decomposition increased with an increase in the Cu/Al ratio to 0.35–0.40. The intensity of absorption bands at 18400 and 25600 cm−1 in the UV-Vis DR spectra increased symbatically. It was hypothesized that the adsorption of NO occurs at Cu+ ions localized in chain copper oxide structures with the formation of mono- and dinitrosyl Cu(I) complexes, and this process is accompanied by the Cu2+...Cu+ intervalence transfer band in the region of 18400 cm−1. The low-temperature activation of NO occurs through the conversion of the dinitrosyl Cu(I) complex into the π-radical anion (N2O2) stabilized at the Cu2+ ion of the chain structure, [Cu2+-cis-(N2O2)], by electron transfer from the Cu+ ion to the cis dimer (NO)2. This complex corresponds to the L → M charge transfer band in the region of 25600 cm−1. The subsequent destruction of the complex [Cu2+-cis-(N2O2)] at temperatures of 150–300°C leads to the release of N2O and the formation of the complex [Cu2+O], which further participates in the formation of the nitrite-nitrate complexes [Cu2+(NO2)], [Cu2+(NO)(NO2)], and [Cu2+(NO3)] and NO decomposition products.  相似文献   

18.
In this study the formation of chromium substituted YBa2Cu4O8 (Y-124) superconductors has been investigated by TG/DTA measurements. The YBa2(Cu1−xCrx)4O8 ceramics with nominal compositions of x=0.01, 0.03, 0.05, 0.10 and 0.20 have been prepared by an aqueous sol-gel method using aqueous mixtures of the corresponding metal acetates and nitrates. Homogeneous precursor gels were obtained by complexing metal ions with tartaric acid. To assist the interpretation of the results obtained the synthesis products were additionally characterized by X-ray powder diffraction (XRD) and resistivity measurements. It was determined that doping the YBa2Cu4O8 phase with chromium has a strong effect on the phase purity and superconducting properties of the synthesis products.  相似文献   

19.
 The most stable structures of V x O y +/V x O y (x=1, 2, y=1–5) clusters and their interaction with O2 are determined by density functional calculations, the B3LYP functional with the 6-31G* basis set. The nature of the bonding of these clusters and the interaction with O2 have been studied by topological analysis in the framework of both the atoms-in-molecules theory of Bader and the Becke–Edgecombe electron localization function. Bond critical points are localized by means of the analysis of the electron density gradient field, ∇ρ(r), and the electron localization function gradient field, ∇η(r). The values of the electron density properties, i.e., electron density, ρ(r), Laplacian of the electron density, ∇2ρ(r), and electron localization function, η(r), allow the nature of the bonds to be characterized, and linear correlation is found for the results obtained in both gradient fields. Vanadium-oxygen interactions are characterized as unshared-electron interactions, and linear correlation is observed between the electron density properties and the V–O bond length. In contrast, O2 units involve typical shared-electron interactions, as for the dioxygen molecule. Four different vanadium–oxygen interactions are found and characterized: a molecular O2 interaction, a peroxo O2 2− interaction, a superoxo O2 interaction and a side-on O2 interaction. Received: 15 October 2001 / Accepted: 30 January 2002 / Published online: 24 June 2002  相似文献   

20.
A sol–gel auto-combustion method was investigated to incorporate small amounts of additives of Cu and Bi uniformly into soft magnetic MnZn-ferrite nanoparticles, which were prepared by Fe(NO3)3·9H2O, Mn(NO3)2 and Zn(NO3)2·6H2O dissolved in water and citric acid. The powder was characterized by the X-ray diffraction analysis and transmission electron microscope method. The effects of nano-particle sized powders in microstructure development and adding CuO–Bi2O3 into MnZn-ferrite on phase formation, densification process as well as magnetic properties were studied by scanning electron microscope and vibrating sample magnetometer techniques. The sample without additive can be sintered well at 930 °C, while the samples with a small amount of the additive can be sintered at less than 900 °C. Obviously, the micron-sized powders exhibited high sintering activity. It was also found that CuO–Bi2O3 additive promoted the growth of grains and improved magnetic properties. The permeability and the saturation magnetization were improved substantially by adding CuO–Bi2O3 into MnZn-ferrite and the sintering temperature was lowered to 875 °C, which may be associated with the redistribution of cations on the tetrahedral (A) sites and octahedral (B) sites within the spinel lattice.  相似文献   

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