Solvent-free oxidation of benzyl alcohol with oxygen using zeolite-supported Au and Au–Pd catalysts

The oxidation of benzyl alcohol to benzaldehyde has been investigated in the absence of solvent using zeolite-supported Au and Au–Pd catalysts. Three zeolites were investigated, ZSM-5, zeolite β and zeolite Y, and these were contrasted with the titanoslicalite TS-1 and TiO₂ as supports. For the Au catalysts the best results are obtained with zeolite β as the support and the conversions were comparable or better than those observed with TiO₂ in terms of turn over frequencies. However, the selectivities observed with the acidic zeolites were lower than the non-acidic TS-1 and TiO₂. This is due to the subsequent reaction of benzaldehyde via acid catalysed reactions to give benzyl benzoate and its dibenzyl acetal, and, in some cases dibenzylether. Initial catalysts were evaluated with a gold loading of 2 wt% and increasing this to 4 wt% showed the expected increase in activity, indicating that there is scope to improve the performance of these catalysts. The most active catalysts were prepared by impregnation and catalysts prepared by deposition precipitation were considerably less active. Introduction of Pd into the catalyst improved the activity without significantly affecting the selectivity.     

Structural analysis of Au/Mg(OH)2 during deactivation by Debye function analysis

Using a Debye function analysis, the presence of icosahedral and face centered cuboctahedral gold in a 1 1 ratio has been found in freshly prepared Au/Mg(OH)₂ catalyst. The results support earlier studies which suggest the icosahedral form to be more stable at small nanometer sizes. Interactions between the gold and the Mg(OH)₂ support appear to be weak, with the gold rapidly coagulating over a period of three months. Re-analysis of the aged sample shows the gold to be mainly in the form of truncated decahedra.     

Au/ZnO and Au/Fe2O3 catalysts for CO oxidation at ambient temperature: comments on the effect of synthesis conditions on the preparation of high activity catalysts prepared by coprecipitation

The preparation of Au/ZnO and Au/Fe₂O₃ catalysts using two coprecipitation methods is investigated to determine the important factors that control the synthesis of high activity catalysts for the oxidation of carbon monoxide at ambient temperature. In particular, the factors involved in the preparation of catalysts that are active without the need for a calcination step are evaluated. The two preparation methods differ in the manner in which the pH is controlled during the precipitation, either constant pH throughout or variable pH in which the pH is raised from an initial low value to a defined end point. Non-calcined Au/ZnO catalysts prepared using both methods are very sensitive to pH and ageing time, and catalysts prepared at a maximum pH = 5 with a short ageing time (ca. 0–3 h) exhibit high activity. Catalysts prepared at higher pH give lower activity. However, all catalysts require a short operation period during which the oxidation activity increases. In contrast, the calcined catalysts are not particularly sensitive to the preparation conditions. Non-calcined Au/Fe₂O₃ catalysts exhibit high activity when prepared at pH ≥ 5. Calcined Au/Fe₂O₃ prepared using the controlled pH method retain high activity, whereas calcined catalysts prepared using the variable pH method are inactive. The study shows the immense sensitivity of the catalyst performance to the preparation methods. It is therefore not surprising that marked differences in the performance of supported Au catalysts for CO oxidation that are apparent in the extensive literature on this subject, particularly the effect of calcination, can be expected if the preparation parameters are not carefully controlled and reported.     

Analysis of the physical properties of an in-vessel composting matrix

Efficient compost production requires a thorough understanding of the process dynamics in terms of the feedstock materials used and the interactions of the physical properties involved. The main properties affecting the composting process are temperature, moisture content, bulk density, porosity and oxygen availability. In this study, the correlations between a selected set of physical properties of a batch-composting matrix were determined. The key physical changes in the composting materials for a blend of woodchips, chicken manure and mixed green vegetables have been monitored during a 36-day composting period in a 200-L rotary drum. The daily measurements conducted on the solid samples included temperature, pH, volatile solids, bulk density, moisture content, free airspace and substrates particle density while the carbon dioxide release was monitored weekly using jar respiration tests. The results from the compost process monitoring were a maximum temperature rise to 66.3 °C over the first 3 days, a marked decrease in free airspace from 76.3% to 40.0% at the end of the process, a variation in average composting material particle density from 1097 kg/m³ to 2325 kg/m³, and an increase in wet bulk density from 255 kg/m³ to 628 kg/m³. Correlations developed among free airspace, wet bulk density, dry bulk density and wet moisture content were in agreement with previously determined equations from literature. Free airspace varied linearly with both dry and wet bulk densities (R² value of 0.89 and 0.95, respectively) while the free airspace-wet moisture content profile followed a fourth degree polynomial trend with a correlation coefficient of 0.63.     

Single-phase gold/palladium catalyst: The nature of synergistic effect

The liquid phase oxidation of glycerol with oxygen has been studied using mono and bimetallic catalysts based on Au and Pd metals supported on activated carbon, in order to study the effect of the metal on the distribution of the products and on activity of catalysts. It was found that by using bimetallic catalysts (Au–Pd) a strong synergistic effect was shown. By using a preformed nucleating centre we were able to obtain a single alloyed phase, which allowed us to address the synergistic effect to the presence of alloyed Au/Pd. The advantage of using this latter catalyst lies not only in the high activity but also in a prolonged catalyst life. Although a partial leaching of palladium and assembling of the particles have been revealed by ICP and HRTEM respectively, activity after 10 re-cycles decreased less than expected (about 10%).     

Free energy barrier for compact chains escaping from a small sphere

In this paper, the process of compact polymer chains escaping from a small sphere to a large one in the view of thermodynamics is investigated in detail based on the pruned-enriched-Rosenbluth method (PERM), which is quite efficient for the three-dimensional polymers on the simple-cubic lattice. In our simulation, three representative states of a polymer chain during the escaping process are studied, and some statistical properties of the chain size and the chain shape, such as mean-square radius of gyration per bond 〈S²〉/N and the shape factor 〈δ^∗〉 are investigated. Our aim is to illuminate how the size and shape of the compact chains change during the escaping process. The changes of 〈S²〉/N and 〈δ^∗〉 are not monotone and it is due to the fact that the chain should stretch itself in the escaping process. In the meantime, some thermodynamic properties are also calculated here. The hole is designed to be small enough to allow only one monomer at a time and it thus reduces the number of allowed chain conformations and breaks contacts between monomers at the beginning of the process. Additionally, we discuss the free energy barrier per bond H₂ − H₁ = ΔH of a compact chain, and here H₂ is the maximum free energy per bond during the process and H₁ is the minimum one when the compact chain is within the small sphere. Averaging free energy barrier over chain length N is convenient for the comparison with different chain lengths. ΔH as a function of chain length N and radius r₁ of the small sphere is also studied and our result shows that ΔH for longer chains is lower means that it is relatively easier for each bond in longer chains to surmount the free energy barrier to escape. Some discussions about the self-avoiding walk (SAW) and swollen chains are also made for the comparison, and our results also show that the restriction of the small sphere on the SAW and the swollen chains is more effective because of their relatively looser intrinsic structure.     

微生物脱砷预处理难冶含砷金矿提金的研究

用化能自养的氧化铁硫杆菌和氧化硫硫杆菌，对河北半壁山含砷金精矿进行了公斤级的预处理氧化脱砷实验．在细菌预处理反应器中的连续和批式脱砷实验表明，目前选育的菌种是有效的．严格控制工艺条件，可以在4天左右便脱砷率高于80％．后续氰化提金实验证实，金的总回收率可达90％以上．用微生物脱砷预处理难冶含砷金矿有金浸出率高、便于固定浸出的砷、免除对环境污染的优点，是有很好应用前景的处理难冶含砷金矿的技术路线．     

接插件的表面处理

综述了接插件连续镀金、钯、锡的电镀工艺，包括设备、镀液和镀层性质。     

Interactions between Cytochrome c and DNA Strands Self-Assembled at Gold Electrode

In this work, we reported the investigation on the interaction between DNA strands self-assembled at gold electrodes and an electron transfer protein, cytochrome c. We observed that cytochrome c exhibited well-defined electrochemistry in both double-stranded and single-stranded DNA films. This suggested that the electron transfer reaction of cytochrome c arose possibly due to the electron hopping along DNA strands rather than wiring along the double helix. We also compared the heterogeneous electron transfer rate of cytochrome c with that of a ruthenium complex, which further confirmed this mechanism.     

Thiophene-based dendronized macromonomers and polymers

The synthesis of thiophene-containing second (G2) and third generation (G3) dendronized macromonomers with methacrylate polymerizable units as well as their corresponding dendronized polymers is reported. The dendrons are prepared from branched thiophene oligomers and are decorated with straight alkyl chains for solubility reasons. The polymerization reactions were done with AIBN as initiator and the polymers were characterized by NMR spectroscopy, elemental analysis and GPC. Molar masses are in the range of 2.2-5.4 × 10⁵ g mol⁻¹ (G2) and 1.3-3.0 × 10⁴ g mol⁻¹ (G3) for different runs. These polymers are investigated by cyclic voltammetry and optical spectroscopy.