Pd–Al interaction at elevated temperatures: a TEM and SAED study

Epitaxially grown Pd particles partly embedded in amorphous Al₂O₃ were subjected to annealing and reductive treatments in the temperature range 523–873 K to induce a possible Pd–Al interaction. The structural, morphological and compositional changes were monitored by transmission electron microscopy and selected area electron diffraction. Formation of Pd₄Al₃ and PdAl alloys has been observed upon annealing in 1 bar He for 1 h at T > 523 K and upon reduction in 1 bar H₂ for 1 h at T ≥ 523 K, respectively. Both alloys appear to be stable up to 873 K, although Pd₄Al₃ shows beginning decomposition at and above 873 K. The stability under oxidative conditions was found to be very similar, a transformation back into metallic Pd sets in for both compounds at around 573–623 K. In agreement with previous studies on Pd/SiO₂, the formation of an amorphous hydride phase and/or a heavily distorted Pd lattice has been detected after reduction in hydrogen at 523 K.     

Ni based catalysts promoted with cerium used in the steam reforming of toluene for hydrogen production

Ni_xMg_6?xAl_1.8Ce_0.2 (with 0 ≤ x ≤ 6) mixed oxides catalysts were prepared by hydrotalcite route. All the oxides were calcined at 800 °C and characterized by different physico-chemical methods. The catalysts are then reduced before their use in the steam reforming of toluene. The XRD and TG/DTA confirmed the formation of the hydrotalcite structure for the non-calcined samples. The N₂ adsorption/desorption results revealed that all catalysts correspond to mesoporous materials. The study by temperature programmed reduction (H₂-TPR) showed that the reducibility of the catalysts is influenced by the nickel content. The CO₂-TPD results showed that the catalyst with high magnesium content present the highest basicity. The Ni₂Mg₄Al_1.8Ce_0.2 shows the best toluene conversion among all the catalysts and it was then compared to a non-promoted catalyst. The spent catalysts were characterized by TPO, TG/DTA and XRD and they didn't reveal any coke formation.     

Layer‐By‐Layer Dendritic Growth of Hyperbranched Thin Films for Surface Sol–Gel Syntheses of Conformal,Functional, Nanocrystalline Oxide Coatings on Complex 3D (Bio)silica Templates

Here, a straightforward and general method for the rapid dendritic amplification of accessible surface functional groups on hydroxylated surfaces is described, with focus on its application to 3D biomineral surfaces. Reaction of hydroxyl‐bearing silica surfaces with an aminosilane, followed by alternating exposure to a dipentaerythritol‐derived polyacrylate solution and a polyamine solution, allows the rapid, layer‐by‐layer (LBL) build‐up of hyperbranched polyamine/polyacrylate thin films. Characterization of such LBL‐grown thin films by AFM, ellipsometry, XPS, and contact angle analyses reveals a stepwise and spatially homogeneous increase in film thickness with the number of applied layers. UV–Vis absorption analyses after fluorescein isothiocyanate labeling indicate that significant amine amplification is achieved after the deposition of only 2 layers with saturation achieved after 3–5 layers. Use of this thin‐film surface amplification technique for hydroxyl‐enrichment of biosilica templates facilitates the conformal surface sol–gel deposition of iron oxide that, upon controlled thermal treatment, is converted into a nanocrystalline (～9.5 nm) magnetite (Fe₃O₄) coating. The specific adsorption of arsenic onto such magnetite‐coated frustules from flowing, arsenic‐bearing aqueous solutions is significantly higher than for commercial magnetite nanoparticles (≤50 nm in diameter).     

Catalysis on oriented ultrathin films of platinum on Al2O3

The selectivity of the hydrogenolysis of methylcyclopentane on model thin film catalysts was investigated and the morphology of the particles was checked in parallel by transmission electron microscopy and transmission electron diffraction. The catalysts were island-stage platinum films of defined orientation obtained by evaporating platinum onto (100)- and (111)-oriented NaCl substrates, backing with Al₂O₃ and dissolving the substrate.The catalysts were quite inactive as long as the single-crystal surface was unchanged, and any increase in activity was accompanied by a change in morphology. The results are compared with those obtained on non-oriented films as well as on bulk single-crystal surfaces.     

Surface reactions on inverse model catalysts: CO adsorption and CO hydrogenation on vanadia- and ceria-modified surfaces of rhodium and palladium

Reducible transition metal oxides are well-known promoters of the hydrogenation of CO on noble metal surfaces. In this study the promotional effect of vanadia and ceria adlayers on Rh and Pd surfaces was investigated with emphasis on the effect of the oxidation state on CO adsorption and catalytic activity. Inverse supported catalysts were prepared by UHV deposition of V and Ce on the noble metal surface (Rh(111), Pd(111) or Rh foil). After oxidation and specified reduction, the reaction kinetics on polycrystalline Rh was measured at atmospheric pressure, and the molecular and dissociative chemisorption of CO on Rh(111) and Pd(111) and the methanation kinetics on Rh(111) were investigated by molecular beam techniques. On Rh(111), the probability of CO dissociation and the reaction rate are enhanced by submonolayer VO _x deposits. Local pressures between 10^-2 and 1 mbar are sufficient to drive the methanation at 573 K with measurable amounts of products, accompanied by significant restructuring of the catalyst surface. Although the reaction on Rh is generally promoted by small quantities of vanadia and ceria, the reaction rates depend strongly on the extent and temperature of hydrogen reduction. The observed increase of the reaction rate by reduction up to 673 K can be correlated to concomitant changes of the structure and composition of the VO _x deposits. If the reduction temperature is raised above 673 K, metallic V is partially dissolved in the bulk, and the resulting V/Rh subsurface alloy exhibits a particularly high activity. Contrary to vanadia, ceria islands on Rh promote the initial reaction only after a low-temperature reduction, but the activity decreases after reduction above 573 K.     

A cervical manikin procedure for chiropractic skills development

Spinal injuries resulting from falls out of tree stands are often associated with concomitant neurologic deficit, prolonged hospitalization, and long-term disability. The purpose of this study was to review the types of spinal injuries that resulted from falls from hunting tree stands. We retrospectively reviewed 27 patients who came to our institution for treatment of spine injuries related to tree-stand accidents between 1981 and 1997. Eleven percent of the falls were alcohol related. Mean height of the fall was 19.6 feet (range, 10 to 35 feet). There were 17 burst fractures, 8 wedge compression fractures, 4 fractures involving the posterior elements, and 1 coronal fracture of the sacral body. Significant neurologic injury occurred in 12 patients (44%). Sixteen patients (59%) had associated injuries. Nine patients (33%) had open reduction, internal fixation, and fusion of their spine fractures. One patient was treated with a halo jacket. The remaining patients were treated in rigid, molded, polypropylene thoracolumbar orthoses or lumbosacral corsets. Accidental falls from tree stands may result in significant spinal fractures often associated with concomitant neurologic injury, extended hospitalization, and permanent disability. Many of these injuries may be prevented through aggressive hunter safety education.     

New resolution algorithm and pretreatments for the two-dimensional bin-packing problem

The two-dimensional bin-packing (2BP) problem involves packing a given set of rectangles A into a minimum number of larger identical rectangles called bins. In this paper, we introduce the concept of dependent orientation items that have special characteristics, and give the formulation that characterizes these items. Then we propose three pretreatments for the non-oriented version of the problem. These pretreatments allow finding optimal packing of some items subsets of the given instance. They enable increasing the total area of the items and consequently the continuous lower bound. Finally, we propose a new heuristic method based on a best-fit algorithm adapted to the 2BP problem. Numerical experiments show that this method is competitive with the heuristic and metaheuristic algorithms proposed in the literature for the considered problem in respect of both the quality of the solution and the computing time.     

Dietary fat effects on hepatic lipid peroxidation and enzymes of H2O2 metabolism and NADPH Generation

The purpose of this study was to determine the effects of dietary fat quantity and fatty acid composition on hepatic H₂O₂-metabolizing systems, activities of NADPH-generating enzymes and lipid peroxidation. Onemonth-old male C57BL/6J mice were fed one of six diets: (i) 5% fat, rich in 18∶2n−6 fatty acid (5% N−6); (ii) 20% fat, rich in 18∶3n−3 (N−3); (iii) 20% fat, rich in 18∶2n−6 (N−6); (iv) 20% fat, rich in 18∶1n−9 (N−9); (v) 20% fat, rich in saturated fatty acids (SAT); and (vi) 20% fat, deficient in essential fatty acids (EFAD); for 11 wk. Comparisons between animal groups receiving different fat quantities showed that activities of glucose-6-phosphate dehydrogenase (G6PDH, EC 1.1.1.49) and malic enzyme (ME, EC 1.1.1.40) and the levels of conjugated dienes were significantly lower in the N−6 than in 5% N−6 group. Conversely, activities of catalase (CAT, EC 1.11.1.6) and seleniumglutathione peroxidase (SeGSHPx, EC 1.11.1.9) were higher in the N−6 than in 5% N−6 group. Among the five dietary groups receiving 20% fat but differing in fatty acid composition, CAT activity was lower in the N−9 group, SeGSHPx activity was lower in the EFAD group, and glutathione reductase (GSSGR, EC 1.6.4.2) activity was higher in the N−6 than in the N−3, N−9, SAT and EFAD groups. The EFAD group had much higher levels of total lipids and conjugated dienes, as well as activities of NADPH-generating enzymes, including G6PDH, ME and isocitrate dehydrogenase (EC 1.1.1.42), than the other four high-fat groups. The hepatic levels of malondialdehyde were not different among the five groups fed 20% fat. In the EFAD group, higher hepatic lipid content can be attributed to higher activities of NADPH-generating enzymes, and the elevation of conjugated diene levels may be related to increased oxygenation of 20∶−6 (Mead acid)via the lipoxygenase/cyclooxygenase pathway. In short, both dietary fat quantity and fatty acid composition selectively affected hepatic H₂O₂-metabolizing systems, activities of NADPH-generating enzymes and lipid peroxidation status.