Understanding silica-supported metal catalysts: Pd/silica as a case study

Supported metal catalysts, particularly noble metals supported on SiO₂, have attracted considerable attention due to the importance of the silica–metal interface in heterogeneous catalysis and in electronic device fabrication. Several important issues, e.g., the stability of the metal–oxide interface at working temperatures and pressures, are not well-understood. In this review, the present status of our understanding of the metal–silica interface is reviewed. Recent results of model studies in our laboratories on Pd/SiO₂/Mo(1 1 2) using LEED, AES and STM are reported. In this work, epitaxial, ultrathin, well-ordered SiO₂ films were grown on a Mo(1 1 2) substrate to circumvent complications that frequently arise from the silica–silicon interface present in silica thin films grown on silicon.     

笼形团簇材料

近年来,在原子、分子和凝聚态两层次之间出现了原子团簇这一重要的学科领域。本文介绍了笼形团簇材料的国内外最新研究进展,分析了笼形团簇材料的研究现状,并对其未来的发展方向进行了展望。     

Catalytic reduction of N2O with CH4 and C3H6 over Ag–Rh/Al2O3 bimetallic catalyst in the presence of oxygen

A study of nitrous oxide (N₂O) reduction with methane (CH₄) and propene (C₃H₆) in the presence of oxygen (5%) over Ag/Al₂O₃, Rh/Al₂O₃ and Ag–Rh/Al₂O₃ catalysts, with Ag and Rh loadings of 5 wt% and 0.05 wt% respectively, has been performed. From the results, it was observed that the Ag–Rh bimetallic catalyst was the most active for both nitrous oxide removal (more than 95%) and hydrocarbon oxidation. This high activity seems to be connected with a synergistic effect between Ag and Rh. The findings from X‐ray diffraction and X‐ray photoelectron spectroscopy studies showed also, that there were no strong interactions (eg alloying) between Ag and Rh. Copyright © 2005 Society of Chemical Industry     

A novel fuzzy clustering algorithm for the analysis of axillary lymph node tissue sections

Recently Fourier Transform Infrared (FTIR) spectroscopic imaging has been used as a tool to detect the changes in cellular composition that may reflect the onset of a disease. This approach has been investigated as a mean of monitoring the change of the biochemical composition of cells and providing a diagnostic tool for various human cancers and other diseases. The discrimination between different types of tissue based upon spectroscopic data is often achieved using various multivariate clustering techniques. However, the number of clusters is a common unknown feature for the clustering methods, such as hierarchical cluster analysis, k-means and fuzzy c-means. In this study, we apply a FCM based clustering algorithm to obtain the best number of clusters as given by the minimum validity index value. This often results in an excessive number of clusters being created due to the complexity of this biochemical system. A novel method to automatically merge clusters was developed to try to address this problem. Three lymph node tissue sections were examined to evaluate our new method. These results showed that this approach can merge the clusters which have similar biochemistry. Consequently, the overall algorithm automatically identifies clusters that accurately match the main tissue types that are independently determined by the clinician.     

Targeting optimum resource allocation using reverse problem formulations and property clustering techniques

Decoupling the constitutive equations from the balance and constraint equations allows for reformulating a conventional forward problem into two reverse problems. The first reverse problem is the reverse of a simulation problem, where the process model is solved in terms of the constitutive (synthesis/design) variables instead of the process variables, thus providing the synthesis/design targets. The second reverse problem (reverse property prediction) solves the constitutive equations to identify unit operations, operating conditions and/or products by matching the synthesis/design targets. Visualization of the problem is achieved by employing recently developed property clustering techniques, which allows a high-dimensional problem to be visualized in two or three dimensions. The clusters by definition satisfy intra-stream and inter-stream conservation through linear “mixing” rules, which allows for the development of consistent additive rules along with their ternary representation.     

Plastic deformation of bcc metal thin foils without dislocation

Heavy plastic deformation of fcc metal thin foils to fracture has been found recently to proceed without involving dislocations, and it results in the formation of high density of vacancy clusters. Thin foil specimens of bcc metals such as V and Mo were plastically deformed to fracture in in situ elongation experiments under an electron microscope. Morphology of thinning and fracture was found to be similar to fcc metals, and no dislocation was observed during heavy deformation. Electron diffraction analysis at the tip of a crack during deformation confirmed a large elastic deformation of up to 5%. Unlike in fcc metal thin foil specimens, point defect clusters were not observed near fractured tips. This difference is attributed to the difference in vacancy reaction, though the deformation in bcc metals without dislocation most likely does produce vacancies.     

Interaction of H2,n-butane and cis-2-butene with Pt and Pt In in NaY: a microcalorimetric study

Pt NaY and Pt In NaY adsorption properties have been compared by using probes like H₂, C₄H₁₀, 2-C₄H₈ and microcalorimetry. It appears that the addition of In to Pt does not change the initial heat of H₂ chemisorption but decreases the initial heat of butane and butene chemisorption.     

AlSn20Cu/Steel双金属板(带)复合轧制过程的厚度匹配

通过对AlSn20Cu/Steel双金属板(带)复合轧制过程变形区变形规律的分析，确定了轧制过程的总变形率与各分层变形率的关系，解决了实际生产中各分层原料的厚度匹配问题。     

Internal-oxide-band formation during oxidation of Ag-Mg alloys

Ag-3a/oMg was oxidized in air over the range of 400–900°C. Internal-oxide bands of MgO formed approximately parallel to the surface, the first band appearing at some finite, but irregular depth below the surface. The region between the surface and the first band appeared to be free of precipitates, but TEM showed that very small clusters, about 50 Å in diameter, formed in the PFZ, causing significant hardness (greater than 300 VHN). The clusters contain more oxygen than that corresponding to stoichiometric MgO. The hardness between oxide bands was also high, but not as high as in the PFZ. The kinetics of thickening of the internal-band region followed the parabolic rate law between 400 and 700° C, with departures from the parabolic law occurring at higher temperatures. The activation energy for the parabolic rate constants was 19.4 Kcal/mol, a value less than the total for oxygen diffusion and oxygen dissolution. The reaction front was planar and parallel to the surface prior to band formation at temperatures of 400–600° C. Nucleation of the first band resulted in nonplanar and nonparallel oxide. Little or no correlation existed between grain boundaries and oxide formation. Nodules of virtually pure silver formed on the surface initially at grain boundaries and subsequently within grains. Nodule formation is attributed to stress-enhanced (resulting from strains associated with precipitation) diffusion of silver to the surface via dislocation pipes. Internal-band formation is discussed in terms of prior data in the literature and various models. It is thought that stress effects (induced by precipitation), nucleation, and clustering of oxygen with Mg play significant roles in causing internal-band formation.     

Run(n=2～7)金属团簇与氧反应的DFT研究

采用密度泛函理论的广义梯度近似(DFT／GGA)，对Run簇(n=2～7)与氧相互作用的几何结构与电子结构及吸附能之间的关系进行讨论。对氧原子及氧分子在Run金属簇上的吸附研究表明：电荷主要是从Ru的5s、4d轨道向O的2p轨道迁移，并使得金属．金属之间的键减弱。比较特殊的是当氧分子在桥位吸附时，Ru与吸附的O2会发生化学反应，并且由于Ru金属轨道的电子向O2的反键πg轨道转移，导致Ru-O之间的键的生成以及O-O之间的键发生断裂。同时，作者也观察到Ru．Ru之间的化学键发生断裂，形成具有原子活性的自由Ru原子，这可以部分解释一旦氧化物种形成，经过一诱导期后，氧化反应会加速进行的实验事实。