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131.
Savinova D. V. Molodkina E. B. Danilov A. I. Polukarov Yu. M. 《Russian Journal of Electrochemistry》2004,40(7):687-694
The formation of an adatom layer on polycrystalline platinum and the three-dimensional nucleation of copper in a copper perchlorate solution are studied by cyclic voltammetry at 0.1 V s–1 while varying potential ranges and by recording potentiostatic current transients. About 0.6 monolayers of copper adatoms are deposited when cycling with anodic limit E
a = 1.35 V, the process is slower than that in an acid sulfate solution. Decreasing E
a accelerates the process (nearly one monolayer forms for E
a = 0.80–0.95 V in a cathodic scan) due to an increased number of active centers (metastable copper oxides) and, probably, to a change in the platinum surface microstructure. Oxygen for copper oxides is presumably supplied by water molecules adsorbed on a monolayer of copper adsorbed atoms and by subsurface oxygen (Oss), which appears on the platinum surface after the destruction of complexes Oss–Pt
n
–ClO4. Both the copper nucleation and the deposit growth accelerate at higher concentrations of copper oxides, which form at low E
a. High cathodic overvoltages decrease the number of active crystallization centers due to reduction or removal of copper oxides. 相似文献
132.
《Magnetic resonance in chemistry : MRC》2018,56(3):190-195
The local distortions and electron paramagnetic resonance parameters for Cu2+ in the mixed alkali borate glasses xNa2O‐(30–x)K2O‐70B2O3 (5 ≤ x ≤ 25 mol%) are theoretically studied with distinct modifier Na2O compositions x. Owing to the Jahn–Teller effect, the octahedral [CuO6]10− clusters show significant tetragonal elongation ratios p ~19% along the C4 axis. With the increase of composition x, the cubic field parameter Dq and the orbital reduction factor k exhibit linearly and quasi‐linearly decreasing tendencies, respectively, whereas the relative tetragonal elongation ratio p has quasi‐linearly increasing rule with some fluctuations, leading to the minima of g factors at x = 10 mol%. The composition dependences of the optical spectra and the electron paramagnetic resonance parameters are suitably reproduced by the linear or quasi‐linear relationships of the relevant quantities (i.e., Dq, k, and p) with x. The above composition dependences are analyzed from mixed alkali effect, which brings forward the modifications of the local crystal‐fields and the electronic cloud distribution around Cu2+ with the variation of the composition of Na2O. 相似文献
133.
D. W. Davidson Y. P. Handa C. I. Ratcliffe J. A. Ripmeester J. S. Tse J. R. Dahn 《Molecular Crystals and Liquid Crystals》2013,570(1-2):141-149
Low-temperature neutron and X-ray diffraction studies show the gas hydrates of oxygen and nitrogen to be structure II (Fd3m), as recently found also for the hydrates of the small argon and krypton molecules. New lattice parameters of three structure I and 14 structure II hydrates from powder X-ray diffraction at 170 K are reported. The thermal expansion coefficient of tetrahydrofuran hydrate was determined from X-ray diffraction at some 50 temperatures between 18 and 263 K and found to be three times as great as for ice near 100 K and 30% higher near 250 K. Lattice parameters qf 40 type II clathrate hydrates are compared at 0°C and found to lie within 0.10 Å of 17.30 Å. 相似文献
134.
Abstract On radiolysis tris(acetylacetonato) cobalt(III) in aqueous solutions is found to get reduced by reaction with (1) hydrated electrons, (2) H atoms, (3) OH radicals and (4) C2H2OH radicals. The bimolecular rate constants for the first three reactions, determined by competition kinetics are: 4 × 1010, 2.3 × 109 and 4.7 × 109 M?1sec?1 respectively. Absorption spectra of the irradiated solutions indicate the formation of bis(acetylacetonato) cobalt(II) from reaction (1), but not from (3). The total cobaltous yield in air-free solutions is given byG(Co++) = 5.6 and 6.5 at pH 6.5 and 1 respectively. It appears that Geaq- ∽ H + GoH ∽ 2.8 in neutral solutions. Considerations of material balance for the primary yields of radiolysis of water suggest the possibility that the so-called independent H-atoms in neutral solutions are probably excited water molecules or ion-pairs. 相似文献
135.
The photoluminescence (PL) properties of ZrO2 have been measured at different temperatures between 7 and 300 K, using various kinds of ZrO2 specimens: bulk crystal melt-grown by a large solar furnace, thermally oxidized zirconium plate (ZrO2 film crystal on Zr ) and nanocrystals (surface area: 35–45m2/g, diameter: 20–30 nm). The results clarify the deep and shallow energy level structures in the energy gap. Reversible UV-laser-light-induced spectral changes are observed for all of the specimens in different specimen-atmospheres (vacuum and O2 gas). The results elucidate the defect-effects of the PL properties and the PL enhancement mechanism in ZrO2 nanocrystals. 相似文献
136.
137.
Ji‐Xin Tian Can Peng Lei Xu Yuan Tian Zun‐Jian Zhang 《Biomedical chromatography : BMC》2013,27(6):775-783
In this report, the in vitro metabolism of Strychnos alkaloids was investigated using liquid chromatography/high‐resolution mass spectrometry for the first time. Strychnine and brucine were selected as model compounds to determine the universal biotransformations of the Strychnos alkaloids in rat liver microsomes. The incubation mixtures were separated by a bidentate‐C18 column, and then analyzed by on‐line ion trap/time‐of‐flight mass spectrometry. With the assistance of mass defect filtering technique, full‐scan accurate mass datasets were processed for the discovery of the related metabolites. The structural elucidations of these metabolites were achieved by comparing the changes in accurate molecular masses, calculating chemical component using Formula Predictor software and defining sites of biotransformation based upon accurate MSn spectral information. As a result, 31 metabolites were identified, of which 26 metabolites were reported for the first time. These biotransformations included hydroxylation, N‐oxidation, epoxidation, methylation, dehydrogenation, de‐methoxylation, O‐demethylation, as well as hydrolysis reactions. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
138.
Auf der Grundlage des Zirkulations-Diffusions-Prinzips wurden zwei Trennrohre für die Hochanreicherung von Gasen enytwickelt. Als Modellgasmischungen dienten H2-N2 Kr-CH4 und Luft. Neben Wasserdampf wurden Methanol- und Äthaanoldämpfe als Treibmittel benutzt. Gute Trennungen wurden in einem nur 20 cm langen Rohr erzielt, dessen Trennspalt horizontal durch Lamellen in kleine Sektionen und durch ein Drahtdiaphragma vertikal in zwei Ringkammern geteilt wird. Drei Rohre dieses Typs wurden in einer rechteckigen Kaskadenanordnung getestet. Die Theorie des Transportes im Trennrohr sowie die Behandlung des hydrodynamischen Problems werden angegeben. Eine Anwendung des beschriebenen Trennrohres zur Isotopentrennung und zur Gashochanreicherung erscheint aussichtsreich. 相似文献
139.
140.
We report here our results on the spectroscopic and elemental analysis of femtosecond (fs) laser-modified regions in polymers of polymethylmethacrylate (PMMA) and polydimethylsiloxane (PDMS) in the context of defect formation and emission in the visible region. Different physical and chemical models are used to explain the changes in modified regions. We found that the emission intensity, recorded from the fs-modified regions of polymers, decreased over time to a constant value. We also demonstrate that these materials are suitable for the preparation of the microstructures en route for light guiding applications. The fs laser-irradiated regions exhibited paramagnetic behavior as was confirmed from electron spin resonance studies through the formation of peroxide-type free radicals. Raman mapping was performed in the modified regions which consisted of defects and found that the modulations in intensity are predominant in the central portion of the structure compared to edges. Elemental analysis has been performed in the modified regions using field emission scanning electron microscope instrument and energy-dispersive X-ray absorption spectroscopy to estimate the percentage contents of individual elements which resulted in defect formation such as paramagnetic and optical centers. 相似文献