High catalytic activity of PdOx/MnO2 for CO oxidation and importance of oxidation state of Mn

PdO_x/MnO₂ has been examined as a catalyst for CO oxidation using a conventional flow reactor at reaction temperatures between 50 and 150°C. In the reaction conditions of GHSV (gashourlyspacevelocity) of 1.22 × 10⁵/h and CO concentration of 2000 ppm, PdO_x/MnO₂ showed higher catalytic activity compared with PdO_x/Mn₂O₃, which had been previously reported as an effective catalyst due to the cooperative action of Pd and Mn₂O₃ for this reaction. The reason for higher activity of PdO_x/MnO₂ than PdO_x/Mn₂O₃ has been investigated using TPR (temperatureprogrammed reduction) and XPS studies. TPR showed that PdO_x/MnO₂ could be reduced by CO at much lower temperature than PdO_x/Mn₂O₃. During the experiment of reduction and oxidation, XPS showed that the valence of Mn in the PdO_x/MnO₂ was between 4+ and 3+, which is higher than that of Mn in the PdO_x/Mn₂O₃ catalyst of which the valence has been reported to be between 3+ and 2+. It is known that in this catalyst system the support supplies oxygen onto Pd, where the oxidation occurs with adsorbed CO, and the ability of the support to provide oxygen improves the performance of the catalyst. Therefore, it was concluded that the readiness of MnO₂ to be reduced with maintaining a higher oxidation state showed higher CO oxidation activity than Mn₂O₃ as support for PdO_x.     

Absorption of NO x in packed column (I)

A mathematical model for an absorption of nitrogen oxides into water in packed column was developed based on the mass-transfer coefficient in packed column and the chemical reaction accompanying NO _x absorption produces HNO₃ and HNO₂ in the liquid phase. The subsequent dissociation of HNO₂ in the liquid-phase results in the formation of HNO₃ and NO gas, and then this NO gas follows to be oxidized by O₂ in air. The important factors influenced on the absorption of NO _x are the oxidation state of NO gas and the partial pressure of nitrogen oxides in the gas. The efficiency of NO _x absorption increases with the increase of the partial pressure of NO _x . The most critical value for using the model is the constant of .The selection of 11×10⁻⁴kg·mol/atm·m²·sec for resonable for this model.     

Influence of mixing cycle on the degree of mixing of calcite‐filled polyethylene upon stretching

The mixing cycle‐dependent degree of dispersion and degree of mixing of a calcite (calcium carbonate) agglomerate in high‐density polyethylene (HDPE), low‐density polyethylene (LDPE), and linear low‐density polyethylene (LLDPE) matrices upon stretching was investigated using three different techniques: mechanical property, morphological behavior, and image analyzer analyses. The mechanical properties analyzed in terms of the tensile strength and maximum elongation resulted in that the second mixing was the best for giving a better property for all systems except the LDPE system, which exhibited no significant difference between the second and third mixings. The morphological behavior of the three compounds were different, but no distinctive difference was observed to differentiate the degree of mixing from system to system. The number‐, weight‐, and z + 1‐average diameters of the air hole and the aspect ratio upon the stretching and mixing cycle were calculated to analyze the degree of mixing of the calcite‐filled composites. As a consequence, no difference in the average diameter of the air hole was obtained among the three systems, but the aspect ratios of the air hole varied significantly. Thus, the degree of dispersion and the degree of mixing may be influenced by the average calcite agglomerate size, the average diameter of the air hole, and the aspect ratio upon stretching and mixing cycles. Those factors would be formed by the difference in chemical characteristics upon various microstructures of polyethylene and its molecular weight and molecular weight distribution. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 311–321, 2003     

Olfactory coding in the perception of semiochemicals

Information processing in the olfactory pathway underlying the perception of semiochemicals by insects is discussed. Both the chemical message for mates and the message for food consist of blends of chemicals. Olfactory receptors in an insect species are tuned to the detection of those compounds which comprise such chemical messages for that species. The classification of receptors as specialists or generalists coincides with two concepts of information processing, i.e., labeled lines and across-fiber patterns, respectively. The olfactory code coming from antennal receptors inPieris brassicae larvae is a combination of labeled lines and across-fiber patterning. When antennae of adult Colorado potato beetles,Leptinotarsa decemlineata, are stimulated by binary mixtures of leaf odor components, the pattern of neural activities in the olfactory receptors shows some separation into two channels, quantitative versus qualitative detection. The separation is complete in the antennal lobe of this beetle.Presented at the Symposium on Insect Chemical Communications: Unifying Concepts. ACS 194th National Meeting, New Orleans, Louisiana, August 31, 1987.     

Methyl tert-butyl ether decomposition over heteropoly acid catalyst in a cellulose acetate membrane reactor

In this study the methyl tert-butyl ether (MTBE) decomposition over H₃PW₁₂O₄₀ was carried out in a cellulose acetate membrane reactor. The permeability of methanol through the cellulose acetate membrane was about 30 and 300 times higher than that of either isobutene or MTBE, respectively. The isobutene selectivity in the fixed bed reactor was only slightly higher than the methanol selectivity due to the side reaction. In the cellulose acetate membrane reactor, however, the isobutene selectivity in the rejected stream was 68% and the methanol selectivity in the permeated stream was up to 97%. The MTBE conversion in the membrane reactor was about 7% higher than that in the membrane-free fixed bed reactor under the same reaction conditions. The enhanced performance of the membrane reactor in this reversible reaction was mainly due to the selective permeation of methanol which resulted in a methanol-deficient condition suppressing MTBE synthesis reaction.     

Morphology-rheology relationship in hyaluronate/poly(vinyl alcohol)/borax polymer blends

In this work, we have prepared bioartificial polymer blends using hyaluronate (HA) as a biological component and poly(vinyl alcohol)-borax association (PVAs) as a synthetic component, and investigated the rheological properties as well as morphology of the blends. When plotted against the blend composition, the rheological properties showed both positive and negative deviation from the linear additive mixing rule depending on thermal history. The blend showed enhanced viscosity at the composition of 20 wt% of HA and 80 wt% of PVAs, when PVA was dissolved at high temperature. The viscosity enhancement was caused by the network formation of HA aggregates in the micrometer scale. In addition, the network structure of HA aggregates was found to be fractal with the fractal dimension of 1.7. As PVA system also forms a network structure in the nanometer scale between hydroxyl groups of PVA and borate anions, the blend system is unique in that it has network structures in both micrometer and nanometer scales in one material. On the contrary, HA formed aggregates but not any network structure in the blend of the same composition but of the negative deviation. In conclusion, we showed that HA/PVAs blend system may have diverse morphology as well as very broad spectrum of rheological properties, and could suggest that the rheology and morphology of HA/PVAs blends can be designed not only by controlling composition but also by controlling thermal and deformation history of the components.     

Characterization and preparation of new multiwall carbon nanotube/conducting polymer composites by in situ polymerization

Composites based on poly(diphenyl amine) (PDPA) and multiwall carbon nanotubes (MWNTs) were prepared by chemical oxidative polymerization through two different approaches: in situ polymerization and intimate mixing. In in situ polymerization, DPA was polymerized in the presence of dispersed MWNTs in sulfuric acid medium for different molar composition ratios of MWNT and DPA. Intimate mixing of synthesized PDPA with MWNT was also used for the preparation of PDPA/MWNT composites. Transmission electron microscopy revealed that the diameter of the tubular structure for the composite was 10–20 nm higher than the diameter of pure MWNT. Scanning electron microscopy provided evidence for the differences in the morphology between the MWNTs and the composites. Raman and Fourier transform IR (FTIR) spectroscopy, thermogravimetric analysis, X‐ray diffraction, and UV–visible spectroscopy were used to characterize the composites and reveal the differences in the molecular level interactions between the components in the composites. The Raman and FTIR spectral results revealed doping‐type molecular interactions and coordinate covalent‐type interactions between MWNT and PDPA in the composite prepared by in situ polymerization and intimate mixing, respectively. The backbone structure of PDPA in the composite decomposed at a higher temperature (>340°C) than the pristine PDPA (～300°C). This behavior also favored the molecular level interactions between MWNT and PDPA in the composite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3721–3729, 2006     

Energy Transfer and Population Inversion in Heavy Metal Oxide Glasses Doped with Tm3+ and Tb3+

Emission properties and energy transfer of PbO–Bi₂O₃–Ga₂O₃–GeO₂ glasses codoped with Tm³⁺ and Tb³⁺ ions were investigated. The 1.48-μm emission due to the Tm³⁺:³H₄→³F₄ transition can be used to amplify the S-band (1460–1530-nm) signal light. With Tb³⁺ addition, the lifetime and emission intensity of the Tm³⁺:³F₄ level decreased sharply via the Tm³⁺:³F₄→Tb³⁺:⁷F_0,1,2 energy transfer. Population densities of the ³F₄ and ³H₄ levels in Tm³⁺ calculated from rate equations clearly verified that population inversion in Tm³⁺ ions became possible with as little as 0.1 mol% of Tb³⁺ addition.     

Generation, Characterization, and Impact of Mesopores in Zeolite Catalysts

Amongst the current developments in the field of hierarchical pore structures, the creation of mesopores in zeolite crystals is the most frequently employed way to combine micropores with mesopores in one material. In this review an overview is presented of the different approaches to generate and characterize mesopores in zeolite crystals and establish their impact on the catalytic action. Mesopores can be created via several routes from which steaming and acid leaching are the most frequently applied. Novel approaches using secondary carbon templates that are removed after synthesis have recently been launched. For the characterization of mesopores, nitrogen physisorption and electron microscopy are commonly used. More recently, it was shown that electron tomography, a form of three-dimensional transmission electron microscopy, is able to reveal the three-dimensional shape, size, and connectivity of the mesopores. The effect of the presence of mesopores for catalysis is demonstrated for several industrially applied processes that make use of zeolite catalysts: the cracking of heavy oil fractions over zeolite Y, the production of cumene and hydroisomerization of alkanes over mordenite, and synthesis of fine chemicals over Y, ZSM-5, and Beta. For these processes, the mesopores ensure an optimal accessibility and transport of reactants and products, while the zeolite micropores induce the preferred shape-selective properties.     

Preparation of alginate/poly(N‐isopropylacrylamide) semi‐interpenetrating and fully interpenetrating polymer network hydrogels with γ‐ray irradiation and their swelling behaviors

Semi‐interpenetrating polymer network (semi‐IPN) and fully interpenetrating polymer network (full‐IPN) hydrogels composed of alginate and poly(N‐isopropylacrylamide) were prepared with γ‐ray irradiation. The semi‐IPN hydrogels were prepared through the irradiation of a mixed solution composed of alginate and N‐isopropylacrylamide (NIPAAm) monomer to simultaneously achieve the polymerization and self‐crosslinking of NIPAAm. The full‐IPN hydrogels were formed through the immersion of the semi‐IPN film in a calcium‐ion solution. The results for the swelling and deswelling behaviors showed that the swelling ratio of semi‐IPN hydrogels was higher than that of full‐IPN hydrogels. A semi‐IPN hydrogel containing more alginate exhibited relatively rapid swelling and deswelling rates, whereas a full‐IPN hydrogel showed an adverse tendency. All the hydrogels with NIPAAm exhibited a change in the swelling ratio around 30–40°C, and full‐IPN hydrogels showed more sensitive and reversible behavior than semi‐IPN hydrogels under a stepwise stimulus. In addition, the swelling ratio of the hydrogels continuously increased with the pH values, and the swelling processes were proven to be repeatable with pH changes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4439–4446, 2006