Structure-sensitive reactions over kinetics

Kinetics of Structure Sensitive Reactions Over Clean Single Crystal Surfaces... 

The previous analysis shown that the initial values of most of the kinetic parameters obtained from DFT calculations provide a good description of the reaction kinetics data collected over a wide range of conditions. The principal difference between the values of the final kinetic parameters used in the model and the initial values obtained from DFT calculations is that the fitted enthalpy changes for the formation of C2Ha transition states involved in cleavage of the C-C bond are lower than the initial values predicted from DFT calculations. This difference may be explained by the structure sensitivity of the system and/or by the inherent error of the DFT calculations. 

The oxidation of CO by either 02 or NO was studied by Peden et al. and Oh et al. over Rh, Pd, Pt,and Ir single crystals (90-92). The CO + 02 reaction was relatively insensitive to the atomic structure of the surface, and the specific activities and kinetic parameters agreed for both crystal surfaces and for alumina-supported catalysts. The Rh surfaces deactivated at high 02 pressures due to the formation of a near-surface oxide (91, 92). On the other hand, the CO + NO reaction was very sensitive to... 

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