| Co-Investigator(Kenkyū-buntansha) |
MIYAO Toshihiro Kanagawa University, Department of Applied Chemistry, Assistant, 工学部, 助手 (90312090)
MORI Wasuke Kanagawa University, Department of Chemistry, Professor, 理学部, 教授 (60029709)
|
|---|
| Budget Amount *help |
¥13,700,000 (Direct Cost: ¥13,700,000)
Fiscal Year 2004: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 2003: ¥4,600,000 (Direct Cost: ¥4,600,000)
Fiscal Year 2002: ¥7,100,000 (Direct Cost: ¥7,100,000)
|
|---|
| Research Abstract |
We have investigated the catalytic behavior as well as adsorption behavior over coordination polymer complexes of Rh(dicarboxilate), Co(bipyridyl) and metal encapsulated silica and titania nanotube catalysts.
When fumalic acid, thelephalic acid, nathalene dicarboxylic acid, mucone acid were used as ligands, Rh dicroboxylic complexes exhibited gas occlusion ability such as H_2, CO, NO, various olefins and pallafines (several molecules per one Rh metal). The amount of occlusion depended on the sizes of ligands as well as absorbent molecules, however, gradual crystallization of the polymer complexes took place, which caused the decrease of the amount of occlusion. H_2-D_2 hydrogen exchange reaction took place as low temperatures as 200 K, and two different exchange mechanisms were observed between dissociatively adsorbed H(a) and D(a) and between D(a) and hydrogen in ligand molecules. Hydrogen exchange and hydrogenation of olefin also took place below room temperatures, where former exchan
… More
ge proceeded only inside the pores of the polymer complexes although the latter exchange proceeded both inside the pores and over outer surfaces of the complexes. The gradual crystallization of the complexes again took place with the repeated catalytic reactions. TEM observation revealed uniform sphere particles rather than sheet structures.
In the case of Co(bipyridyl) coordination polymer complexes, a large amount of NH_3 occlusion was observed, which accelerated the reduction of NO by NH_3, showing a important role of pore structures for NO-NH_3 reaction to form N_2 selectivery.
Selective permeation property of H_2 took place progressively by higher temperature evacuation of Pt-SiO_2 nanotubes, indicating the formation ultra micro pores inside the network of silica walls. There existed a few ten nm Pt particles inside the tubes and sub-nm Pt clusters inside the silica networks of the wall, and the latter Pt might be responsible for the characteristic catalytic behavior in CO-H_2 reaction. Pt encapsulated TiO_2 nanotubes exhibited one order of magnitude larger TOF in CO-H_2O and CO-H_2 reactions than conventional impregnated Pt/TiO_2 catalysts. More than 90% selectivity for methanol formation was acheved in CO-H_2 reaction in the case of nanotube catalysts. Exceptionally strongly adsorbed CO, which was observed by FT-IR may be responsible for these unique catalytic behavior of these nanotube catalysts. Less
|
