Structure of activated complex of CO2 formation in a CO + O2 reaction on Pd(110) and Pd(111).
Examinations of CO2 formed during steady-state CO oxidation reactions were performed using infrared (IR) chemiluminescence. The CO2 was formed using a molecular-beam method over Pd(110) and Pd(111). The CO2 formation rate is temperature dependent under various partial pressure conditions. The temperature of the maximum formation rate is denoted as TSmax. Analyses of IR emission spectra at surface temperatures higher than TSmax showed that the average vibrational temperature (TVAV) is higher for Pd(111) than for Pd(110). The antisymmetric vibrational temperature (TVAS) is almost equal on both surfaces. These results suggest that the activated CO2 complex is more bent on Pd(111) and straighter on Pd(110). Furthermore, the difference in the TVAV value was small for surface temperatures less than TSmax. The TVAS value was much higher than TVAV on both surfaces. These phenomena were observed only when the surface temperature was lower than TSmax: they became more pronounced at lower temperatures, suggesting that the activated complex of CO2 formation is much straighter on both Pd surfaces than that observed at higher surface temperatures. Combined with kinetic results, the higher CO coverage at the lower surface temperatures is inferred to be related to the linear activated complex of CO2 formation.
Nakao
Kenji
K
Institute of Materials Science, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573, Japan.
Ito
Shin-ichi
S
Tomishige
Keiichi
K
Kunimori
Kimio
K