島津 省吾

Ru-hectorite catalysts with various interlayer distances have been prepared and characterized by X-ray diffraction (XRD), infrared spectroscopy and temperature programmed desorption (TPD). It was found that the interlayer distance depended on the H2-treatment temperature of the catalysts. Hydrogenation of various olefins was studied using these catalysts. The catalytic activity was shown to depend on the interlayer distances. © 1987.

Resin supported palladium metal was prepared from [Pd(NH3)4]-form sulfonic resin by treatment: with H2. The CO adsorption and H2-D2equilibration reaction were greatly promoted by treatment above 373 K where Pd(II) was reduced to Pd(O) as indicated by XPS study. The reaction rate is of the 2.5th order with respect to the metal sites. © 1987 Akadémiai Kiadó.

Various polymer-supported rodium complexes were prepared using commercially available cation-exchange resins and chelate resins and the catalytic behaviour with respect to methanol carbonylation in the presence of methyl iodide promoter was investigated. RhCl3 was simply loaded on functionalized chelate resins such as a polyethyleneimine type (CR-20) and a pyrrolidine type (NR2), and on sodium-form sulphonic resins (AMNa and HPNa) by a cation-exchange method in ethanol solution. The catalysts were treated with hydrogen and/or carbon monoxide before use. Low-pressure methanol carbonylation was studied at 373-473 K in a circulating system in the ranges 6.65-25.9 kPa for carbon monoxide and 2.66-11.3 kPa for methanol with methyl iodide. A sulphonic resin-supported rhodium, Rh/AMNa, showed the highest activity and methyl acetate was produced with a maximum selectivity of 82.5%. The reaction rate observed for the CR-20-supported rhodium is approximately first order with respect to methyl iodide and carbon monoxide and 0.5 order in methanol. An IR study of Rh/CR-20 suggests that the active species of rhodium (I) -carbon monoxide is formed after carbon monoxide treatment and an X-ray photo-electron spectroscopic study of Rh/CR-20 showed the formation of rhodium (II) species after hydrogen treatment. © 1987.

The process of the ligand release and the reduction of [Pd(NH 3) 4]-form sulfonic resin has been studied by chemical analysis, X-ray photoelectron spectroscopy and adsorption techniques. The removal of ammonia ligands remarkably increased with hydrogen treatment above 353 K, and was complete at around 393 K. It is suggested that the released ammonia partly transfers to -SO 3 - groups to form -SO 3NH 4 groups as the reduction proceeds. The dispersion of the metal particles prepared by hydrogen reduction ranged from. 0.11 to 0.31 depending on the loading concentration of the palladium cation. The metal particles are considered to be entrapped in the pores of the resin. The formation of cationic palladium sites by the low temperature reduction is also suggested. © 1986 The Chemical Society of Japan.

Nickel (II) ions were supported in the layer structure of lithium taeniolite, Li (Mg2Li) (Si4O10) F2, by ion-exchange method. Intercalated nickel metal catalyst was prepared by reducing iu with hydrogen.<BR>The thermal properties and the inter-layer spacings were studied by DTA, TG and XRD. The Ni-form taeniolite has expanded d001 spacings in the hydrated states which were stabilized by the nickel substitution.<BR>Catalytic activities for the hydrogenation, isomerization and cracking of cis-2-butene were en hanced by hydrogen treatment above 200°C. The selectivity for the hydrogenation decreased with the increase in the reduction temperature, while the cracking reaction were promoted. The hydrocracking to form C2-compounds was observed as well as methane formation by the terminal C-C bond splitting which is characteristic of nickel metal catalyst.

Molybdenum(IV) complexes of sequential polypeptides, (Gly2Cys)nand (Gly3Cys)mwere prepared, and their catalytic activities examined in the electron transfer reduction (by NaBH4) of acetylene. These molybdenum complexes had excellent catalytic activity in comparison with that of N-carbobenzyloxy-L-cysteine methyl ester. © 1983.