Active sites of Cu-ZSM-5 for the decomposition of acrylonitrile

The catalytic decomposition of acrylonitrile (AN) over Cu-ZSM-5 prepared with various Cu loadings was investigated. AN conversion, during which the nitrogen atoms in AN were mainly converted to N₂, increased as Cu loading increased. N₂ selectivities as high as 90–95% were attained. X-ray diffraction measurements (XRD) and temperature-programmed reduction by H₂ (H₂-TPR) showed the existence of bulk CuO in Cu-ZSM-5 with a Cu loading of 6.4 wt% and the existence of highly dispersed CuO in Cu-ZSM-5 with a Cu loading of 3.3 wt%. Electron spin resonance measurements revealed that Cu-ZSM-5 contains three forms of isolated Cu²⁺ ions (square-planar, square-pyramidal, and distorted square-pyramidal). The H₂-TPR results suggested that in Cu-ZSM-5 with a Cu loading of 2.9 wt% and below, Cu⁺ existed even after oxidizing pretreatment. The activity of AN decomposition over Cu/SiO₂ suggested that CuO could form N₂, but, independent of the CuO dispersion, nitrogen oxides (NO_x) were formed above 350 °C. Cu⁺ and the square-pyramidal and distorted square-pyramidal forms of Cu²⁺ showed low activity for AN decomposition. Temperature-programmed desorption of NH₃ suggested that N₂ formation from NH₃ proceeded on Cu²⁺, resulting in the formation of Cu⁺. The Cu⁺ ions were oxidized to Cu²⁺ at around 300 °C. Thus, high N₂ selectivity over Cu-ZSM-5 with a wide range of temperature was probably attained by the reaction over the square-planar Cu²⁺, which can be reversibly reduced and oxidized.     

The effects of R-75,317 on antiglomerular basement membrane glomerulonephritis in rats

Platelet-activating factor (PAF) is a potent inflammatory mediator which is released by various inflammatory cells and produced by certain tissues, including the kidney. PAF has been shown to increase glomerular permeability to protein and to decrease glomerular filtration rate (GFR) by contracting mesangium. On the basis of these observations, it has been suspected that PAF may play a role as mediator of glomerular damage in glomerular nephritis. To examine this possibility, we studied the effects of a specific PAF antagonist, R-75,317, on the development of an experimental model of anti-glomerular basement membrane (anti-GBM) glomerulonephritis. Glomerulonephritis was initiated by injecting rabbit anti-rat GBM serum into rats. Proteinuria gradually developed after serum injection, plateaued at week 2, and remained at the high level of week 2 throughout the experimental period (6 wk). Chronic treatment with R-75,317 (10 mg/kg/day i.p.) tended to delay the onset of proteinuria and significantly accelerated the recovery phase. Creatinine clearance (Ccr) fell to 40% at week 3. R-75,317 treatment completely prevented this decline of Ccr. Histological changes in this model (glomerular hypertrophy, proliferation of mesangial matrix and interstitial fibrosis) were also ameliorated by the R-75,317 treatment. The results suggest that PAF may play a role in the development of glomerulonephritis and that PAF antagonists could be used in the treatment of human renal disease. Based on a paper presented at the Third International Conference on Platelet-Activating Factor and Structurally Related Alkyl Ether Lipids, May 1989.     

Characterization of Silicon Carbide–Silicon Nitride Composite Ultrafine Particles Synthesized Using a CO2 Laser by Silicon-29 Magic Angle Spinning NMR and ESR

The structure of silicon carbide–silicon nitride (SiC–Si₃N₄) composite particles synthesized using a CO₂ laser was studied by magic angle spinning nuclear magnetic resonance (MAS-NMR) and electron spin resonance (ESR). The structure around Si atoms changed by introducing N. C atoms around Si were substituted by N atoms, and N-rich configurations around Si atoms increased stepwise as the N content increased. The low N content composite particles consisted of mainly SiC phase containing dissolved N. N atoms were partly present in β-SiC microcrystal and partly in the grain boundary layer in the particle. N atoms were tetrahedrally surrounded by four Si atoms in β-SiC microcrystal and were trivalent state bonded to three Si atoms in the grain boundary layer. The high N content particles consisted of SiC, Si₃N₄, and amorphous phases, whose amount depended on N content.     

Role of tungsten in promoting selective reduction of NO with CO over Ir/WO3–SiO2 catalysts

Catalytic hydrogenation of naphthalene to decalin was studied over a carbon-supported rhodium catalyst in supercritical carbon dioxide solvent at 333 K, and the results were compared with those in an organic solvent. cis-, trans-Decalin and tetralin were formed from the beginning of the reaction in supercritical carbon dioxide. Higher concentration of hydrogen in carbon dioxide solvent and on the active site, and also the suppression of desorption of partially hydrogenated tetralin molecules from the active site would be responsible for higher selectivity to cis-decalin in supercritical carbon dioxide than that in an organic solvent.     

Effect of polymer density on polyethylene hollow fiber membrane formation via thermally induced phase separation

Microporous high‐density polyethylene (HDPE) and low‐density polyethylene (LDPE) hollow fiber membranes were prepared from polyethylene–diisodecyl phthalate solution via thermally induced phase separation. Effect of the polyethylene density on the membrane structure and performance was investigated. The HDPE membrane showed about five times higher water permeability than the LDPE membrane because it had the larger pore and the higher porosity at the outer membrane surface. The formation of the larger pore was owing to both the initial larger structure formed by spinodal decomposition and the suppression of the diluent evaporation from the outer membrane surface due to the higher solution viscosity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 471–474, 2004     

Studies on phase separation rate in porous polyimide membrane formation by immersion precipitation

Phase separation rate during porous membrane formation by immersion precipitation was investigated by light scattering in a polyimide/N‐Methylpyrrolidone (NMP)/water system. In the light scattering measurement, plots of scattered intensity against scattered angle showed maxima in all cases, which indicated that phase separation occurred by a spinodal decomposition (SD). Characteristic properties of the early stage of SD, such as an apparent diffusion coefficient D_app and an interphase periodic distance Λ, were obtained. The growth process of Λ was also followed by light scattering. The growth rate had the same tendency as D_app when water content in the nonsolvent bath and the polymer concentration in the cast solution were changed. The pore size of the final membrane increased with decreasing water content, which was opposite to the tendency of Λ growth rate. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 292–296, 2003     

Silica-supported cobalt catalysts for the selective reduction of nitrogen monoxide with propene

Catalytic behavior of silica-supported transition metals for NO reduction with propene in the presence of oxygen was investigated. While both silica and cobalt oxides did not show any activity for the selective NO reduction, impregnated CoO/SiO₂ prepared from cobalt acetate showed good activity although the preparation conditions had significant effect on the activity. It was suggested that highly dispersed surface Co²⁺ ions on silica are responsible for the catalytic activity.     

Fractionation and enrichment of CLA isomers by selective esterification with Candida rugosa lipase

A commercial product of CLA contains almost equal amounts of cis-9,trans-11 (c9,t11)-CLA and trans-10,cis-12 (t10,c12)-CLA. We attempted to enrich the two isomers by a two-step selective esterification using Candida rugosa lipase that acted on c9,t11-CLA more strongly than on t10,c12-CLA. An FFA mixture containing CLA isomers was esterified with an equimolar amount of lauryl alcohol in a mixture of 20% water and the lipase. When the esterification of total FA reached 50%, two isomers were fractionated in a good yield: t10,c12-CLA was enriched in FFA, and c9,t11-CLA was recovered in lauryl esters. The FFA were esterified again to enrich t10,c12-CLA. At 27.3% esterification of total FA, the t10,c12-CLA content in FFA increased to 64.8 wt% with 89.3% recovery: The ratio of the content of t10,c12-CLA to that of two isomers was 95.9%. Lauryl esters obtained by the single esterification were employed for enrichment of c9,t11-CLA. After the esters were hydrolyzed, the resulting FFA were esterified again with lauryl alcohol. At 62.0% esterification of total FA, the c9,t11-CLA content in lauryl esters increased to 73.3 wt% with 79.4% recovery: The ratio of the content of c9,t11-CLA to that of two isomers was 95.6%. In a 600-g-scale purification, molecular distillation was effective in separating the reaction mixture into lauryl alcohol, FFA, and lauryl ester fractions.     

Electrochemical micromachining using a solid electrochemical reaction at the metal/β″-Al2O3 microcontact

A simple solid state technique for electrochemical micromachining of metal substrates using a metal ion conductor (Na-β″-Al₂O₃) was proposed. The fundamental solid electrochemical cell consists of a (anode) metal substrate (M = Ag, Cu, Zn, and Pb)/pyramidal Na-β″-Al₂O₃/Ag (cathode) system, where the contact diameter between M/Na-β″-Al₂O₃ was extremely small, on the order of a few micrometer. Under an applied electric field, the metal substrate was electrochemically oxidized to metal ions (Mⁿ⁺) at the M/Na-β″-Al₂O₃ microcontact. These Mⁿ⁺ ions migrated into the Na-β″-Al₂O₃. As a result of continuous electrolysis, the metal substrate was locally consumed at the microcontact, and thus solid state electrochemical micromachining was accomplished. As expected, the machining size or depth depended on the electrolysis conditions (current, operating time) and the apex configuration of pyramidal Na-β″-Al₂O₃. Moreover, the scanning of the Na-β″-Al₂O₃ pyramid during electrolysis produced a fine patterned metal substrate. In the present paper, solid state electrochemical micromachining was performed for several metal substrates, and its advantages and disadvantages vis-a-vis the conventional electrochemical micromachining method are discussed in detail.