Sorption of hydrogen by MCM-41 molecular sieves containing nanoparticles of 3d metals or their oxides

It was shown that the sorptive capacity for hydrogen in composites based on MCM-41 molecular sieves and nanoparticles of the oxides of 3d metals or the metals themselves at 77 K and 1 atm is determined both by the surface area and by the volume of the micropores of the samples and does not depend on the nature of the 3d metal (Ni, Co, Cu) or its degree of oxidation. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 5, pp. 265–270, September–October, 2006.     

Effect of antimony on the reduction of anodic Pbo_2 film on Pb-Sb alloys in sulfuric acid solution

The reduction processes of anodic PbO2 films formed on Pb-Sb alloys in 4.5mol·dm-3 H2SO4 solution at 1.4 V(vs.Hg/Hg2SO4) for 1 h have been investigated by pho-tocurrent method,chronoamperometry,linear sweep voltammetry as well as X-ray diifractornetry.It was found that the reduction of most of the β-PbO2 and part of the α-PbO2 to PbSO4 can be completed within I s between 0.9 V and 1.0 V(vs.Hg/Hg2SO4) and proceeds much faster than that of the remaining a-PbO2 into photoactive α·PbOx (1相似文献   

Studies on isothermal kinetics of some reactions of aluminum oxides and hydroxides

Thermal decomposition and hydrothermal reactions of aluminum oxides and hydroxides were studied. The starting material was gibbsite pretreated by grinding in different ways. Sixteen kinetic models were fitted and the rate constants were estimated at different temperatures. Mechanical activation of the starting gibbsite had an effect on the reactivity of samples in several subsequent reactions.A new quantity, the relative residual variance is defined for comparison of different linearized models, and it is proposed as a criterion of fit. This was applied in making statistics in order to find the well-fitting models.

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Zusammenfassung Es wurden die thermische Zersetzung und hydrothermische Reaktionen von Aluminiumoxiden und -hydroxiden untersucht. Das Ausgangsmaterial war Gibbsit, welches durch Zerkleinern auf verschiedene Weise vorbereitet wurde. Es wurden sechzehn kinetische Modelle angewendet und bei verschiedenen Temperaturen die Gesch-windigkeitskonstanten geschätzt. Die mechanische Aktivierung des Ausgangsmateriales Gibbsit beeinflu\t die Reaktivität der Proben in einigen Folgereaktionen.Für den Vergleich verschiedener Linearisationsmodelle wurde eine neue Grö\e, die relative Restvarianz definiert, die als Kriterium für die Anpassungsgüte vorgeschlagen wird. Dies wurde bei statistischen Untersuchungen angewendet, um die bestangepa\ten Modelle zu finden.

     

Zur Präparation und Struktur gemischtvalenter Niob-Wolframoxide der Zusammensetzung (Nb,W)17O47

Preparation and Structure of Niobium Tungsten Oxides (Nb,W)₁₇O₄₇ with Mixed Valency The formal substitution of 2Nb⁵⁺ by Nb⁴⁺ or W⁴⁺, respectively, and W⁶⁺ leads to tungsten niobium oxides (Nb,W)₁₇O₄₇ with mixed valency. The phases Nb_8-nW_9+nO₄₇ with n = 1 to 5 could be obtained by heating (1 250°) mixtures of NbO₂ or WO₂, respectively, with Nb₂O₅ and WO₃. The products crystallize with the structure of Nb₈W₉O₄₇. This is proved by X-ray powder diffraction and transmission electron microscopy. A further decrease of the Nb-content results in two-phase products.     

Nb-Ta, Nb-Mo and Nb-V oxides prepared from hybrid organic-inorganic precursors

New hybrid organic-inorganic materials based on group 5 elements and a well-defined polymeric matrix have been prepared and used as precursors for Nb-Ta and Nb-Mo mixed oxides. In this non-conventional but easily accessible route to multimetallic oxides, a copolymer of N,N-diallyl-N-hexylamine and maleic acid was synthesised and used as matrix to stabilise inorganic species generated in solution from (NH₄)₆Mo₇O₂₄·4H₂O, NH₄VO₃, (gu)₃[Nb(O₂)₄] and (gu)₃[Ta(O₂)₄]. Solid-state studies indicate that the homogeneity of the blends can be kept up to about 0.5 mol Nb^V and Ta^V and 0.25 mol V^V per mol of repeat units of the copolymer. The calcination conditions of these homogeneous hybrid precursors were optimised to produce Nb-Mo, Nb-Ta and Nb-V oxides. While the thermal treatment of the Nb-V hybrid blends led only to a mixture of different phases, the characterisation of the final phases by X-ray diffraction (XRD) proved the formation of pure Nb₂Mo₃O₁₄ and showed that Nb-Ta oxides could be synthesised as single phases corresponding to a continuous series of solid solutions.     

Decay kinetics of benzophenone oxide in the liquid phase

The kinetics of self-termination of benzophenone oxide (BPO) in the liquid phase was studied by flash photolysis. The extinction coefficient of BPO (ε) was found to be virtually independent of the solvent nature, ε=(1.9±0.1)·10³ L mol⁻¹ cm⁻¹. The rate constant of the BPO self-temination increases from 1.8·10⁷ (MeCN) and 7.4·10⁷ (C₆H₆) to 1.5·10⁹ (n-decane) and 2.0·10⁹ L mol⁻¹ s⁻¹ (n-pentane) at 293±2 K. Solvation of BPO promotes a polar state of the molecule in MeCN and C₆H₆. In nonpolar hydrocarbons, a great contribution is made by the biradical structure resulting in an increase in the rate constant and a shift of the absorption maximum to the long-wave region (from 410 nm in MeCN to 425 nm inn-pentane). In solutions of benzene and acetonitrile, benzophenone oxide reacts with the parent diazo compound with a rate constant of (2–4)·10⁵ L mol⁻¹ s⁻¹ (293±2 K) along with the self-termination. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1329–1332, July, 1998.     

Thin-film TiO2 electrode surface characterization upon CO2 reduction processes

The effect of electrochemical reduction of CO₂ on the structure and morphology of titanium(IV) oxide thin films was examined after a fixed-potential bulk electrolysis process. Films deposited on ITO (Indium-Tin Oxide) substrates were used as the working electrodes and 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF₄]) as solvent and as supporting electrolyte. Grazing incidence X-ray diffraction analysis performed before and after the electrolysis process indicated no microstructural changes of the anatase films. X-ray photoelectron spectroscopy revealed peaks associated with adsorbed carbonate ions at 288 eV and CO₂ species at 293 eV, whereas Ti2p peaks displacements for CO₂-saturated TiO₂/ITO surfaces in [BMIm][BF₄] revealed chemical bonding effects. Auger electron spectroscopy revealed a high carbon content on CO₂-exposed films, and suggested a strong chemisorption of CO₂ and CO₃²⁻ species on the TiO₂/ITO surface in [BMIm][BF₄] solvent system. A significant decrease in carbon content after bulk electrolysis indicated that the CO₂ electroreduction process is not controlled by either diffusion or by adsorption of CO₂ on the TiO₂/ITO electrode surface.     

Syntheses based on nitrile oxides

Interaction of aromatic nitrile oxides with bis-trimethylsilylthiodiimide results in 2-amino-4-aryl-1,2,3,5-oxathiadiazoles, the first representatives of a new class of heterocyclic compounds.For Part 2, see ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 742–743, April, 1993.     

LnCu2O4(Ln=Gd,Nd)电子结构的XPS研究

用XPS测定了LnCu2O4(Ln=Gd, Nd)的内层和价层电子能谱,观察到LnCu2O4中稀土金属的3d电子结合能比相应的稀土金属简单氧化物的3d结合能低0.8～0.9 eV,而Cu的2p电子结合能比CuO的高0.4～0.5 eV,因此推断在LnCu2O4的Ln－O－Cu链中存在Cu→O→Ln电荷转移.XPS分析还表明LnCu2O4的Cu原子上有较低的电荷密度,但不存在混合价态.此外,通过比较价电子能谱,发现NdCu2O4的Ln 4f Cu 3d O 2p价带中心比GdCu2O4的价带中心向Fermi能级移近了3.4 eV,而且NdCu2O4的价带谱更窄.