Oxygen adsorption and oxidation reactions on Au(2 1 1) surfaces: Exposures using O2 at high pressures and ozone (O3) in UHV

Nanosized gold particles supported on reducible metal oxides have been reported to show high catalytic activity toward CO oxidation at low temperature. This has generated great scientific and technological interest, and there have been many proposals to explain this unusual activity. One intriguing explanation that can be tested is that of Nørskov and coworkers [Catal. Lett. 64 (2000) 101] who suggested that the “unusually large catalytic activity of highly-dispersed Au particles may in part be due to high step densities on the small particles and/or strain effects due to the mismatch at the Au-support interface”. In particular, their calculations indicated that the Au(2 1 1) stepped surface would be much more reactive towards O₂ dissociative adsorption and CO adsorption than the Au(1 1 1) surface. We have now studied the adsorption of O₂ and O₃ (ozone) on an Au(2 1 1) stepped surface. We find that molecular oxygen (O₂) was not activated to dissociate and produce oxygen adatoms on the stepped Au(2 1 1) surface even under high-pressure (700 Torr) conditions with the sample at 300-450 K. Step sites do bind oxygen adatoms more tightly than do terrace sites, and this was probed by using temperature programmed desorption (TPD) of O₂ following ozone (O₃) exposures to produce oxygen adatoms up to a saturation coverage of θ_O = 0.90 ML. In the low-coverage regime (θ_O ? 0.15 ML), the O₂ TPD peak at 540 K, which does not shift with coverage, is attributed to oxygen adatoms that are bound at the steps on the Au(2 1 1) surface. At higher coverages, an additional lower temperature desorption peak that shifts from 515 to 530 K at saturation coverage is attributed to oxygen adsorbed on the (1 1 1) terrace sites of the Au(2 1 1) surface. Although the desorption kinetics are likely to be quite complex, a simple Redhead analysis gives an estimate of the desorption activation energy, E_d, for the step-adsorbed oxygen of 34 kcal/mol and that for oxygen at the terraces near saturation coverage of 33 kcal/mol, values that are similar to others reported on Au surfaces. Low Energy Electron Diffraction (LEED) indicates an oxygen-induced step doubling on the Au(2 1 1) surface at low-coverages (θ_O = 0.08-0.17 ML) and extensive disruption of the 2D ordering at the surface for saturation coverages of oxygen (θ_O ? 0.9 ML). Overall, our results indicate that unstrained step sites on Au(2 1 1) surfaces of dispersed Au nanoparticles do not account for the novel reactivity of supported Au catalysts for CO oxidation.     

Thermodynamic parameters of Bi2Sr2CaCu2O8+δ thin film prepared by molecular beam epitaxy

Bi₂Sr₂CaCu₂O_8+δ (Bi2212) thin film is an important superconducting material ascribed to its high transition temperatures and low toxicity, but the application of Bi2212 thin films is limited due to the appearances of intergrowth and impurity phases. To achieve high-quality Bi2212 thin film by molecular beam epitaxy (MBE), the oxidizing gas pressure and substrate temperature are the key parameters. Here, the phase formation in Bi-based thin films grown by MBE was studied as a function of oxidizing gas pressure and substrate temperature. Furthermore, the thermodynamic parameters have been investigated through enthalpy change. This study indicates that the substrate temperature was increased with the enhancing of ozone partial pressure when the composition ratio is fixed, Bi2212 single phase can be formed. Moreover, the chemical stability decreases in the order of Bi₂Sr₂CuO_6+δ > Bi2212 > Bi₂Sr₂Ca₂Cu₃O_10+δ.     

Synergetic effect of ozone and ultrasonic radiation on degradation of chitosan

Under conditions of continuous ozone gas application and constant ultrasonic radiation (UR), chitosan was effectively degraded. The existence of a synergetic effect of ozone and ultrasonic radiation on the degradation of chitosan was demonstrated by means of determination of viscosity-average molecular weight. The efficiency of the ozone and ultrasonic radiation treatment compared with acid hydrolysis on degradation of chitosan was investigated. In addition, the structure of the degraded chitosan was characterized by FT-IR and ¹³C NMR spectral analyses. The whole initial chitosan's monomer structure still existed in the resulting degraded chitosan with different low molecular weight. The pilot study of the chemical stability of the degraded chitosan was carried out. There was no significant change of the total degree of deacetylation (DD) of degraded chitosan compared with the initial chitosan. The combined O₃/UR technique is promisingly suitable for scale-up manufacture of low-molecular-weight chitosan.     

气相中O3与HSO自由基间的氢键复合物

气相中O3与HSO自由基之间的相互作用及其反应在大气化学中非常重要.在DFT-B3LYP/6-311++G**和MP2/6-311++G**水平上求得O3+HSO复合物势能面上的稳定构型,B3LYP方法得到了三种构型(复合物Ⅰ,Ⅱ和Ⅲ),而MP2方法只能得到一种构犁(复合物Ⅱ).在复合物Ⅰ和Ⅲ中,HSO单元中的1H原子作为质子供体.与O3分子中的端基O原子作为质子受体相互作用,形成红移氢键复合物;而在复合物Ⅱ中,虽与复合物Ⅰ和Ⅲ中具有相间的质子供体和质子受体,却形成了蓝移氢键复合物.B3LYP/6-311++G**水平上计算的单体间相互作用能的计算考虑了基组重甍误差(BSSE)和零点振动能(ZPVE)校正,其值在-3.37到-4.55 kJ·mol-1之间.采用自然键轨道理论(NBO)对单体间相互作用的本质进行了考查,并通过分子中原子理论(AIM)分析了三种复合物中氢键的电子密度拓扑性质.     

New insights about the electrochemical production of ozone

Ozone is a rather attractive oxidant, it is very efficient in the oxidation of pollutants and in the killing of pathogens and does not generate any hazardous waste during its use. Its generation has been constantly sought in an effective way, focusing on obtaining high concentrations of ozone at the lowest possible cost. Recently, electrochemical production of ozone show advantages over conventional corona discharge generation, since this technology do not need very high voltages, feeding oxygen or pure air or dissolving the ozone into wastewater to be treated. However, it is still at early development stage and there is still a long way to reach the high technology readiness levels needed to complete its value chain. Equipment considerations and operation conditions are the key points that need to be understood in order to increase efficiently. Recent novelties in the state of the art of research are summarized in this work.     

Thermal, ozone and gamma ageing of styrene butadiene rubber and poly(ethylene-co-vinyl acetate) blends

Ageing behaviour of SBR/EVA blends due to the effects of heat, ozone, and gamma radiation was studied with reference to blend ratio, three crosslinking systems (sulfur, peroxide and mixed) and a compatibiliser (SEBS-g-MA). It was found that an increase in the EVA content of the blends enhanced the ageing characteristics. Among the different crosslinking systems, a peroxide cured system exhibited the best retention of properties even after severe ageing. Tensile strength of peroxide cured SBR/EVA blends increased slightly after ageing for three days at 70 °C due to continued crosslinking, whereas tensile strength of all blends decreased on ageing at 100 °C. Compatibilisation with SEBS-g-MA improved the thermal, gamma and water ageing resistance of SBR/EVA blends.     

A study on the effects of ozone treatment on the properties of raw and degummed mulberry silk fabrics

Ozone is a powerful oxidizing agent and is widely used in various applications, which includes bleaching of cotton. Its application on the processing of silk is non-existent. Research studies on degumming and bleaching of silk reveal that almost no work involving ozone has been carried out. Therefore a study was carried out to understand the effects of process parameters namely wet pickup, pH and time in the ozone treatment of raw and degummed mulberry and tassar silk fabrics on their properties. This paper reports on the effects of ozone treatment on the mulberry silk fabrics. The study was extended with a view to compare the ozone treatment with soap degumming and hydrogen peroxide treatment carried out on raw and degummed mulberry silk fabrics, respectively. The treatment results in increase in yellowness index and amino group content and decrease in breaking strength and elongation, weight and flexural rigidity. The results obtained are substantiated with tyrosine content, scanning electron micrographs and infrared spectroscopy of the treated materials. The effect of pH on the treatment is maximum up to pH 4 and then decreases. The treatment is more severe when the wet pickup used is 50% compared to that of 10 and 100%. With respect to treatment time, though the severity increases with time, it is maximum during the first 10 min of the treatment. Soap degumming of raw silk fabric results in lower yellowness index and flexural rigidity and lesser loss in breaking strength and elongation compared to that of ozone treated material. There is not much of difference between ozone and hydrogen peroxide treatments of degummed silk fabric except for the lower yellowness index obtained in the latter case.     

Ozone treatment for mercury determination in white wines

A method was developed for the generation of mercury vapour by means of cold-vapour flow-injection atomic absorption spectrometry (FI-CV-AAS) from white wine samples after ozonation as sample pre-treatment. Two different reactors designs for sample ozonation were developed and investigated. The limit of detection and the limit of quantification were, respectively, 0.5 and 1.7 μg l⁻¹, and the relative standard deviation (n=10) was 2% for a concentration of 50 μg l⁻¹ and 7% for a concentration of 5 μg l⁻¹. The pre-treatment with ozone has allowed to reduce drastically the amount of chemical reagents (e.g. carrier agent and reducing agent) used in the FI-CV-AAS system. The mercury content of wine samples was also determined by FI-CV-AAS after pre-concentration in the presence of HNO₃ and H₂O₂. In general, there was no significant difference among data obtained from both methodologies, but pre-treatment with ozone is much faster.     

Degradation of Furfural by UV/O3 Technology

Furfural in aqueous solution was treated by UV/O3 method.The results show that the removal rate of furfural is severely enhanced and the synergism phenomenon appears when ultraviolet and ozone are present together.The influences of experimental parameters such as pH,the intensity of light and the negative-positive ions on furfural degradation were investigated.The results indicate that furfural(300 mg/L) is almost completely degraded after 3 h under the optimum conditions.The intermediate in the furfural de...