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51.
Hiroshi Onishi 《Catalysis Surveys from Japan》2002,6(1-2):1-8
The present account describes first time examples of scanning tunneling microscope (STM) visualization of reaction intermediates on a metal oxide surface. The topographic response of reactant-adsorbed TiO2(110) surfaces to a temperature increment or to a pressure increment was monitored as a sequence of STM images. Acetates thermally decomposing to ketene were resolved in a temperature-jump STM observation. The kinetics of the acetate consumption was determined on the number of acetates resolved in the microscope images and agreed with the macroscopic rate law of ketene production. A pressure-jump study revealed how a chemisorbed carboxylate (RCOO-) is exchanged by another carboxylate (R'COO-) supplied from the ambient vapor phase. An impinging R'COOH was immobilized on the top of a RCOO- and then squeezed itself into the monolayer of the RCOO-. One of the carboxylates in the squeezed state returned to the vapor phase via the immobilized state. 相似文献
52.
In this work, the optical and structural properties of high k materials such as tantalum oxide and titanium oxide were studied by spectroscopic ellipsometry, where a Tauc-Lorentz dispersion model based in one (amorphous films) or two oscillators (microcrystalline films) was used. The samples were deposited at room temperature by radio frequency magnetron sputtering and then annealed at temperatures from 100 to 500 °C. Concerning the tantalum oxide films, the increase of the annealing temperature, up to 500 °C does not change the amorphous nature of the films, increasing, however, their density. The same does not happen with the titanium oxide films that are microcrystalline, even when deposited at room temperature. Data concerning the use of a four-layer model based on one and two Tauc-Lorentz dispersions is also discussed, emphasizing its use for the detection of an amorphous incubation layer, normally present on microcrystalline films grown by sputtering. 相似文献
53.
The effect of the cation concentration, hydrolysis temperature, and composition in the CeO2–ZrO2 system on the direct precipitation of ceria–zirconia solid solutions and the structure of the precipitates from acidic aqueous solutions of (NH4)2Ce(NO3)6 and ZrOCl2 by hydrolysis under hydrothermal conditions were investigated. Nanometer-sized (8–10 nm) ceria–zirconia solid solution particles in a composition range of 0 to 60 mol% ZrO2 were directly precipitated from the solutions with total metal cation concentration less than 0.2 mol/dm3 by simultaneous thermal hydrolysis at 150–240°C. The crystalline phase of the precipitates gradually changed from cubic and/or tetragonal to monoclinic with increasing the cation concentration of the solution from 0.2 to 0.8 mol/dm3 at the starting composition of 50 mol% ZrO2 under hydrolysis condition of 150°C for 48 h, which was attributed to decrease in the supply of hydrolyzed Ce component caused by decrease in the hydrolysis ratio of (NH4)2Ce(NO3)6. Ceria–zirconia solid solutions containing large amount of ZrO2 maintained high specific surface area and small-sized crystallite after heat-treatment at 900–1000°C for 1 h. 相似文献
54.
以SnCl4·5H2 O为主要原料 ,用溶剂热技术在油酸体系中成功地合成了球形SnO2 纳米微粒 ,在无水乙醇体系中合成了菱形的SnO2 纳米微粒 .通过X射线粉末衍射 (XRD) ,选区电子衍射 (SAED)和透射电镜 (TEM )对两种产物进行了表征 ,并对两种产物的形成机理进行了分析 .透射电镜 (TEM)结果表明 :在油酸体系中得到了平均尺寸约为 3.5nm的球形SnO2 纳米微粒 ,此微粒趋向于特殊高的比表面积 ,适合于作气敏探测器材料方面的应用 相似文献
55.
We have used the periodic quantum-mechanical method with density functional theory at the B3LYP level in order to study TiO2/Sn doped (1 1 0) surfaces and have investigated the structural, electronic and energy band properties of these oxides. Our calculated relaxation directions for TiO2 is the experimental one and is also in agreement with other theoretical results. We also observe for the doped systems relaxation of lattice positions of the atoms. Modification of Sn, O and Ti charges depend on the planes and positions of the substituted atoms. Doping can modify the Fermi levels, energy gaps as well as the localization and composition of both valence and conduction band main components. Doping can also modify the chemical, electronic and optical properties of these oxides surfaces increasing their suitability for use as gas sensors and optoelectronic devices. 相似文献
56.
XPS measurement revealed that the original state of TiO2 was changed to Ti2O3 and TiO by ion bombardment. TiO2 decreased and Ti2O3 increased at the initial stage. TiO increased at a later stage than Ti2O3. Each of them saturated after enough sputtering time.A formulation was proposed in order to explain the change of XPS spectra for oxides as a function of ion sputtering time. This formulation was based on reaction equations that contain two reduction processes (from TiO2 to Ti2O3 and from Ti2O3 to TiO), and sputtering effects. Using four fitting parameters (two reduction coefficients, sputtering yield and information depth), the present formula was fitted to the experimental results. The fitting results agree satisfactorily with the experimental results. The calculation shows that the reduction coefficient from TiO2 to Ti2O3 is about ten times larger than that from Ti2O3 to TiO. This calculation predicts that surface composition of an oxide that is changed by ion bombardment will reach a different value depending on its bulk composition. Moreover, the present formulation can determine the chemical states of compounds changed by ion bombardment. 相似文献
57.
Erzs bet Ill s Etelka Tomb cz 《Colloids and surfaces. A, Physicochemical and engineering aspects》2003,230(1-3):99-109
The ionic strength dependence of humic acid (HA) adsorption on magnetite (Fe3O4) was investigated at pH 5, 8 and 9, where variable charged magnetite is positive, neutral and negative, respectively. The adsorption studies revealed that HA has high affinity to magnetite surface especially at lower pH, where interacting partners have opposite charges. However, in spite of electrostatic repulsion at pH 9 notable amounts of humate are adsorbed. Increasing ionic strength enhances HA adsorption at each pH due to charge screening. The dominant interaction is probably a ligand-exchange reaction, nevertheless the Coulombic contribution to the organic matter accumulation on oxide surface is also significant under acidic condition. The results from size exclusion chromatography demonstrate that the smaller size HA fractions enriched with functional groups are adsorbed preferentially on the surface of magnetite at pH 8 in dilute NaCl solution. 相似文献
58.
S. Mentus Dijana Jelić Veselinka Grudić 《Journal of Thermal Analysis and Calorimetry》2007,90(2):393-397
Thermal decomposition of lanthanum nitrate to lanthanum oxide was carried out by both temperature programmed heating (TPH)
and citrate-gel combustion. The temperature programmed heating was carried out under flow of oxidizing (air), neutral (nitrogen)
and reducing (25 vol.% hydrogen+argone mixture) gases, and the processes were controlled by simultaneous thermogravimetry
and differential thermal analysis. It was shown that hydrogen atmosphere helps to reduce temperatures of all decomposition
steps. The results of TPH were utilized to check the nature of residues in the products of lanthanum nitrate-to-oxide conversion
performed via citrate-gel combustion technique. 相似文献
59.
The electronic states of the Cr overlayers on TiO2(0 0 1) surfaces have been investigated using angle-resolved and resonant photoemission spectroscopy with synchrotron radiation. At lower coverages, Cr deposition on TiO2(0 0 1) creates two well separated in-gap emissions due to the formation of surface Ti3+ (3d1) ions and Cr3+ (3d3) ions. At higher coverages, the in-gap emission is developed into the 2-peak-structure emission of Cr 3d character. The corresponding state is considered to be of metallic nature from the viewpoint of the high ability of oxygen adsorption, but has no Fermi edge, indicating a possibility of forming small Cr clusters on TiO2(0 0 1) at this stage. 相似文献
60.