Effects of support and additive on oxidation state and activity of Pt catalyst in propane combustion

The effects of support and additive on the oxidation state and catalytic activity of Pt catalyst in the low temperature propane combustion were systematically investigated on Pt/MgO, Pt/Al₂O₃ and Pt/SiO₂–Al₂O₃. The catalytic activity varied much with both support materials and additives. The catalyst on the more acidic support showed higher activity, and the catalytic activity on every support materials increased as the electronegativity of additives increased, while some additives decreased the activity. The oxidation state of platinum, estimated by white line intensity of Pt L_III-edge XANES spectrum, also varied with the support and additives, and additives with higher electronegativity greatly prevented the platinum from its oxidation under oxidising atmosphere. Among almost all the catalysts with various supports and various additives, a clear relationship was observed between the oxidation state of platinum and the catalytic activity; the more metallic platinum showed higher activity. Thus, it was concluded that the total electrophilic/electrophobic property derived from those of the support and additive controls the oxidation state of platinum, which intensively affects the catalytic activity; i.e. higher electrophilic property provides less oxidised platinum, resulting in high catalytic activity. The mechanism of this effect was also discussed on the basis of thermochemical data, and it was proposed that the electrophobic materials promote the noble metal oxidation since the noble metal oxo-anion such as PtO^δ− is more stabilised with electrophobic cation.     

Functional metal-porphyrazine derivatives and their polymers, 10. Secondary fuel cells based on oxygen reduction on platinum electrode modified by polymers and metal-phthalocyanines

Secondary fuel cells based on oxygen reduction of platinum electrode modified by polymers and metal-phthalocyanine (Mt = Fe(III), Co(II), Ni(II), and Cu(II)) were studied. The discharge curves for the platinum electrode modified by poly(2-vinylpyridine) (or polystyrene) and Co-phthalocyanine in 30% KOH aqueous solution, for a 30 min charge at 500 μA, followed by a 100 μA discharge showed a stable plateau at about ?0.24 V SCE (Saturated Calomel Electrode). The open circuit voltage (vs. Zn) of the cell was 1.2 V, and the discharge capacity was of 46 A · h/kg. For this battery there was no significant decay in its characteristics after more than 30 charge-discharge cycles. In Mt-phthalocyanines, the values decreased in the order of Co(II) > Fe(III) > > Cu(II) > Ni(II). From a cyclic voltammogram for the electrode modified by the polymer and Co-Pc, the cathodic reactions were discussed.     

Functional monomers and polymers, 64. Synthesis of poly-β-alanine from β-alanine, β-alanyl-β-alanine,and β-alanyl-β-alanyl-β-alanine 4-dodecanoyl-2-nitrophenyl esters

Active 4-dodecanoyl-2-nitrophenyl esters of β-alanine, β-alanyl-β-alanine, and β-alanyl-β-alanyl-β-alanine were prepared, and tried to polymerize in various solvents. Nonpolar solvents were found to be convenient for the polycondensation reaction. The yield of the polycondensation was high for the monopeptide ester, and less for the dipeptide and tripeptide esters. The effect of temperature on the polycondensation reaction was also studied.     

Vinyl polymerization by metal complexes. XVIII. Kinetics of the polymerization of acrylonitrile initiated by imidazole-copper-(II) complexes

A study on the kinetics and mechanism of the polymerization of acrylonitrile initiated by imidazole and 2-substituted imidazole-copper-(II) complexes was made in dimethyl sulfoxide solution at 40–70°C. The rate of polymerization, Rp, could be expressed as follows: The overall activation energies of these polymerization processes are in a range from 14.2 to 69.1 KJ mole^-1. From the data of electronic spectra and electron paramagnetic resonance, it was confirmed that the polymerization in question could be initiated by free radicals which were formed by the reduction of copper-(II) complex to copper-(I) complex, and the latter formed a new complex with polyacrylonitrile resulted.     

Contrasting effects of water-soluble and water-insoluble dietary fibers on bile acid conjugation and taurine metabolism in the rat

The effect of the type of dietary fiber on the bile acid and taurine metabolism was examined in rats. Diets containing 10% of various water-soluble fibers (citrus pectin, konjak mannan, guar gum) as compared to a fiber-free diet increased biliary excretion of total bile acids. In contrast, water-insoluble dietary fibers (cellulose, corn bran, chitin; 10% in the diets) as well as cholestyramine (5% in the diet) considerably, decreased bile acid excretion. Water-soluble dietary fibermediated increases in bile acid excretion were totally attributable to increases in glycine-conjugates. Thus, these fibers greatly increased by the bile acid glycine-to-taurine ratio (G/T). Excretio of glycine conjugates decreased more than that of taurine conjugates in rats fed various water-insoluble dietary fibers. As a results, G/T in rats fed water-insoluble fibers was significantly lowered as compared to G/T in animals fed a fiber-free diet. Cholestyramine did not affect the G/T ratio of bile acids. Fecal bile acid excretion and the activities of hepatic cholesterol 7α-hydroxylase (EC 1.14.13.17) in rats fed various water-soluble dietary fibers approximately doubled as compared to the respective values for rats fed a fiber-free diet. Whereas cholestyramine greatly increased these parameters, water-insoluble fibers did not significantly affect them. Various water-soluble fibers decreased hepatic concentration and urinary excretion of taurine as well as the activity of hepatic cysteine dioxygenase (EC 1.13.11.20). In contrast, water-insoluble fibers considerably increased hepatic taurine concentrations and enzyme activities. The parameters for taurine metabolism were unaffected by cholestyramine. It was suggested that the types of dietary fiber affected hepatic taurine synthesis and thus modified bile acid glycine/taurine ratios.     

Oxidation kinetics for <Emphasis Type="Italic">cis</Emphasis>-9,<Emphasis Type="Italic">trans</Emphasis>-11 and <Emphasis Type="Italic">trans</Emphasis>-10,<Emphasis Type="Italic">cis</Emphasis>-12 isomers of CLA

The autoxidation processes of the cis-9,trans-11 (c9,t11) and trans-10,cis-12 (t10,c12) isomers of CLA were separately observed at ca. 0% RH and different temperatures. The t10,c12 CLA oxidized faster than the c9,t11 isomer at all tested temperatures. The first half of the oxidation process of t10,c12 CLA obeyed an autocatalytic-type rate expression, but the latter half followed first-order kinetics. On the other hand, the entire oxidation process of c9,t11 CLA could be expressed by the autocatalytic-type rate expression. The apparent activation energies and frequency factors for the autoxidation of the isomers were estimated from the rate constants obtained at various temperatures based on the Arrhenius equation. The apparent activation energies for the CLA isomers were greater than those for the nonconjugated n−6 and n−3 PUFA or their esters. However, the enthalpyentropy compensation held during the autoxidation of both the CLA and PUFA. This suggested that the autoxidation mechanisms for the CLA and PUFA were essentially the same.     

Bonelike Hydroxyapatite Induction by a Gel-Derived Titania on a Titanium Substrate

Gel-derived titania coating on commercial pure (c.p.) titanium induces hydroxyapatite formation onto its surface from a simulated body fluid (SBF, a metastable calcium phosphate solution). The induced apatite is similar to bone apatite in that it is poorly crystallized, calcium-deficient, and carbonate-containing. Furthermore, the carbonate (CO^2–3) groups go into the apatite lattice and lie at the positions of PO^3–4 and OH^– to replace these ionic groups, resembling the (CO^2–3) groups of bone apatite. Therefore, the apatite induced by the gel-derived titania is said to be bonelike. A chemical stimulation, stemming from abundant hydroxyl groups and negative charges at the surface of the titania gel, is believed to be responsible for the bonelike apatite induction. The potential of bone-bonding is predicted for the gel-derived titania, for it is an efficient bonelike apatite inducer in the SBF.     

Studies on syntheses and permeabilities of special polymer membranes

Summary The permeation and separation characteristics of methanol/n-pentanol systems and n-propanol/n-heptane systems through nylon 12 membranes were studied by changing the feed composition of the binary organic mixtures. These characteristics were discussed from the viewpoints of physical and chemical nature of the permeating molecules and the membrane.     

Kinetic study on the first stage during thermal degradation of polystyrene

The kinetic parameters of the first stage of polystyrene degradation have been investigated to elucidate the reaction mechanisms using the flow reactor system. The decrease in molecular weight of polystyrene was recorded at minute intervals over the temperature range 310°–390°C. Generally, the first and second stages were observed by thermogravimetric analysis (t.g.a.), however in the early stage of the degradation volatile yields of at least 5% occurred. Therefore, using t.g.a. analysis it is difficult to detect this earlier stage. It became evident that the first stage in the earlier part of the reaction could be detected by g.p.c. analysis. We have observed the hidden kinetic parameters of the nature of the first stage of the polystyrene degradation. The results indicate that the main chains were degraded randomly with the small quantitative volatile groups in the first stage and the rates of decrease in molecular weight in the first stage against reaction temperatures were evaluated as log k_s = 12.0 ? 41300/RT.     

Development of AAS resin by the emulsion–suspension polymerization method

In order to improve the weatherability of acryonitrile—styrene—butadiene rubber graft polymer (ABS resin), an attempt was made to develop a resin (AAS resin) in which acrylic rubber of good weatherability was used instead of butadiene rubber. First, by copolymerizing dicyclopentenyl-methacrylate (DCP-MA,3%) with butyl acrylate, crosslinked acrylic rubber was obtained. This also introduced grafting sites into the rubber. Next, methods of graft copolymerizing styrene and acrylonitrile with this rubber were examined. An emulsion–suspension polymerization method was developed in which the initial stage of the polymerization, emulsion polymerization, changed into suspension polymerization during the process. By this method of polymerization, rubber particles were combined and enlarged, bringing about a graft-type resin with high impact resistance. This polymerization method is industrially useful because particle-shaped resins are obtained without the need of a salting-out process. The AAS resin, obtained in this way, has much improved weatherability over ABS resin and shows strength equal to that of ABS resin. © 1992 John Wiley & Sons, Inc.