A velocity map ion-imaging study on ketene photodissociation at 208 and 213 nm: Rotational dependence of product angular anisotropy

Photodissociation dynamics of ketene following excitation at 208.59 and 213.24 nm have been investigated using the velocity map ion-imaging method. Both the angular distribution and translational energy distribution of the CO products at different rotational and vibrational states have been obtained. No significant difference in the translational energy distributions for different CO rotational state products has been observed at both excitation wavelengths. The anisotropy parameter beta is, however, noticeably different for different CO rotational state products at both excitation wavelengths. For lower rotational states of the CO product, beta is smaller than zero, while beta is larger than zero for CO at higher rotational states. The observed rotational dependence of angular anisotropy is interpreted as the dynamical influence of a peculiar conical intersection between the B-1(1) excited state and (1)A(2) state along the C-S-I coordinate.

CO adsorption and correlation between CO surface coverage and activity/selectivity of preferential CO oxidation over supported Ag catalyst: an in situ FTIR study

In situ IR measurements for CO adsorption and preferential CO oxidation in H-2-rich gases over Ag/SiO2 catalysts are presented in this paper. CO adsorbed on the Ag/SiO2 pretreated with oxygen shows a band centered around 2169 cm(-1), which is assigned to CO linearly bonded to Ag+ sites. The amount of adsorbed CO on the silver particles ( manifested by an IR band at 2169 cm(-1)) depends strongly on the CO partial pressure and the temperature. The steady-state coverage on the Ag surface is shown to be significantly below saturation, and the oxidation of CO with surface oxygen species is probably via a non-competitive Langmuir Hinshelwood mechanism on the silver catalyst which occurs in the high-rate branch on a surface covered with CO below saturation. A low reactant concentration on the Ag surface indicates that the reaction order with respect to Pco is positive, and the selectivity towards CO2 decreases with the decrease of Pco. On the other hand, the decrease of the selectivity with the reaction temperature also reflects the higher apparent activation energy for H-2 oxidation than that for CO oxidation.

On the correlation between microstructural changes of Ag-H-ZSM-5 catalysts and their catalytic performances in the selective catalytic reduction of NOx by methane

The silver catalyzed, selective catalytic reduction (SCR) of nitrogen oxides (NOx) by CH4, is shown to be a structure-sensitive reaction. Pretreatment has a great affect on the catalytic performances. Upon thermal treatment in inert gas stream, thermal induced changes in silver morphology lead to the formation of reduced silver species of clusters and particles. Catalysis over this catalyst indicates an initially higher activity but lower selectivity for the CH4-SCR of NOx Reaction induced restructuring of silver results in the formation of ill-defined silver oxides. This, in turn, impacts the adsorption properties and diffusivity of oxygen over silver catalyst, results in the decrease in activity but increase in selectivity of Ag-H-ZSM-5 catalyst for the CH4-SCR of NO.. (c) 2004 Elsevier B.V. All rights reserved.