温度对还原增感立方体氯化银乳剂中光电子衰减的影响

利用微波介电检测技术,测得还原增感立方体氯化银乳剂中自由光电子与浅束缚光电子衰减行为随还原增感温度的变化。实验发现还原增感温度变化会引起增感中心陷阱作用的变化:当还原增感温度较低时,增感中心起空穴陷阱作用,延缓光电子衰减;还原增感温度较高时,增感中心起深电子陷阱作用,加速光电子衰减。由此,我们得到了确定最佳增感温度的依据。     

Self-assembled monolayers of a disulphide-derivatised cobalt-porphyrin on gold

A self-assembled monolayer (SAM) of a novel cobalt(II)porphyrin disulphide derivative was prepared on flat gold(1 1 1) electrode. Evidence for surface modification was provided by electrochemical reductive desorption of the monolayer and ellipsometry, consistent with a coverage of 2.5 × 10⁻¹⁰ mol cm⁻² and a thickness of 13 Å, respectively. Both results support the presence of SAMs where the molecules share an intermediate position between perpendicular and flat orientation. Scanning tunnelling microscopy have also proven the formation of CoPSS SAMs, however high-resolution images could only be obtained when the CoPSS molecules were diluted in an hexanethiol SAM. The electrocatalytic activity of the surface confined Co-porphyrin was evaluated for the oxygen reduction. Voltammetric data indicate that reaction involves two electrons consistent with the formation of hydrogen peroxide. Under similar experimental conditions the data obtained for an iron-porphyrin analogue points for a full reduction of dioxygen to water.     

Charge reduction and regeneration in K+, Na+, Mg2+, Ni2+ and Co2+-exchanged Wyoming Bentonite

Controlled calcination of ion-exchanged Wyoming Bentonite in the presence and absence of ammonia leads to layer charge reductions. Detailed chemical analyses of both unexchangeable and exchangeable species lead to the conclusion that in no case is there migration of the original interlamellar cations into the octahedral region of the layers although, in terms of ionic radius alone, Mg²⁺, Ni²⁺ and, possibly Co²⁺, might be expected to do so. The production of unexchangeable Mg, Ni or Co, is identified as resulting from high temperature hydrolysis leading to hydroxide or oxide formation.     

Performance of solvothermally prepared Ga2O3-Al2O3 catalysts for SCR of NO with methane

The solvothermal reaction of mixtures of aluminum isopropoxide (AIP) and gallium acetylacetonate (Ga(acac)₃) directly yielded the mixed oxides of γ-Ga₂O₃-Al₂O₃. In the solvothermal synthesis, the crystal structure of mixed oxides was controlled by the initial formation of γ-Ga₂O₃ nuclei. The mixed oxides prepared in diethylenetriamine have extremely high activities for selective catalytic reduction (SCR) of NO with methane as a reducing agent. With increasing crystallite size of the spinel structure, the catalytic activity increased. The ratio of the amount of methane consumed by combustion to total methane conversion was proportional to the density of acid sites on the surface of the mixed oxides. The mixed oxide catalysts prepared in diethylenetriamine had lower densities of acid sites and showed a higher methane-efficiency for CH₄-SCR than those prepared in other solvents. These catalysts maintained their high activity even when the reaction was carried out under the severe conditions (i.e., high space velocity and low NO concentration).     

Kinetic investigation of the chlorine reduction reaction on electrochemically oxidised ruthenium

The rate and mechanism of the electroreduction of chlorine on electrooxidised ruthenium has been investigated with focus on the effect of solution pH. Current/potential curves for the reduction process in solutions with constant chloride concentration of 1.0 mol dm⁻³ and varying H⁺ concentration have been obtained with the use of the rotating disk electrode technique (RDE). It was found that the chlorine reduction rate is highly inhibited in solutions with high H⁺ concentrations and that it can be satisfactorily described by the Erenburg mechanism, previously suggested for the chlorine evolution on RuO₂ and RTO. The expression of the kinetic current as a function of chlorine and H⁺ concentration was obtained by solving the elementary rate equations of the kinetic mechanism. The kinetic constants obtained from the correlation of the kinetic current expression to the experimental data were used to simulate the dependence of the surface coverages and elementary reaction rates on overpotential.     

钛矿渣电热法制取钛硅合金时直流电作用的实验研究

本文研究了实验条件下钛矿渣直流电硅热法制取钛硅合金时直流电对渣中TiO2还原贫化的作用．研究表明：直流电所特有的电解还原和金属液滴电泳沉降对渣中TiO2的还原及合金微粒的沉降均有促进作用外加直流电可使渣中TiO2贫化速度、合金中钛含量、合金收得率、钛回收率升高，合金中硅含量、残渣中TiO2含量降低．半工业性试验结果与此类似．     

Mechanism for the reduction of NOx on Rh/sulfated titanias

Titanias of different surface areas have been sulfated and used as supports of Rh oxide for the selective catalytic reduction of nitrogen oxides. Only the sulfation of TiO₂ of large surface areas gives strong Br?nsted acid sites, retaining pyridine up to 773 K. Low surface area anatase is unable to retain sulfates. The catalytic activities measured at 523 K, increase with the number of acid sites, and then reach a plateau, showing the intervention of acidity in the SCR. This is true only for Rh but not for Pt. The investigation of the elemental steps on Rh/sulfated TiO₂ by in situ diffuse reflectance spectroscopy permits to clarify a few points: the oxidation of propene, presumably to acetaldehyde, occurs by the reaction with nitrates adsorbed on the support. The further oxidation of this intermediate by NO₂ yields an isocyanate, which can be hydrolysed to ammonia.