| Budget Amount *help |
¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 1999: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 1998: ¥2,500,000 (Direct Cost: ¥2,500,000)
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| Research Abstract |
The electrocatalytic activities of metals for the small molecule reactant of COィイD22ィエD2 were investigated by in-situ infrared spectroscopy. The various products were formed from COィイD22ィエD2, such as CO, formate, methane, ethylene, and alcohols, etc. in aqueous solutions. Distributions of products are depended on electrode metals.Two electron reductive products, CO and formate are produced first, then hydrocarbons are produced from CO. Oxalate was formed in stead of formate in non-aqueous media.
1. The selectivity of CO/oxalate was investigated in non-aqueous solution. Active electeodes, such as Au, produce CO and inactive electrodes, such as Pb, produce oxalate. While, Pt, an active electrode, produces mainly oxalate. (1) Infrared spectroscopy revealed the surface of Pt was fully covered in the course of COィイD22ィエD2 reduction with CO, which would prevent adsorption of COィイD22ィエD2-anion redical, intermediate.
2. Hydrocarbons are main products on Cu electeodes. The distributions of hydrocarbons depend on the orientation of Cu single crystal electrodes. Methane is mainly formed at (111) surface, while ethylene is mainly formed at (100) surface. Adsorbed CO, intermediate to hydrocarbons, is investigated on various surfaces of Cu single crystal electrodes by infrared spectroscopy. (1) Different types of CO adsorbed on Cu electrodes were observed and assigned. The infrared band at 2050 cmィイD1-1ィエD1 is assigned to CO adsorbed on (100) terrace and the band at 2075 cmィイD1-1ィエD1 is to that at (100) step and/or at (111) step. CO adsorbs on (111) terrace and expresses the reductive reactions but shows no infrared bands. CO adsorbed on (111) may be infrared inactive, for example, adsorbed parallel to the metal surface. (2) Different types of CO adsorption would contribute different distributions of hydrocarbon products on various surfaces.
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