Density functional theory study of nitrous oxide decomposition over Fe- and Co-ZSM-5

Iron- and cobalt-exchanged ZSM-5 are active catalysts for the dissociation of nitrous oxide. In this study, density functional theory was used to assess a possible reaction pathway for the catalytic dissociation of N₂O. The active center was taken to be mononuclear [FeO]⁺ or [CoO]⁺, and the surrounding portion of the zeolite was represented by a 24-atom cluster. The first step of N₂O decomposition involves the formation of [FeO₂]⁺ or [CoO₂]⁺ and the release of N₂. The metal-oxo species produced in this step then reacts with N₂O again, to release N₂ and O_2. The apparent activation energies for N₂O dissociation in Fe-ZSM-5 and Co- ZSM-5 are 39.4 and 34.6 kcal/mol, respectively. The preexponential factor for the apparent first-order rate coefficient is estimated to be of the order 107 s^-1 Pa^1-. Although the calculated activation energy for Fe- ZSM-5 is in good agreement with that measured experimentally, the value of the preexponential factor is an order of magnitude smaller than that observed. The calculated activation energy for Co-ZSM-5 is higher than that reported experimentally. However, consistent with experiment, the rate of N₂O decomposition on Co-ZSM-5 is predicted to be significantly higher than that on Fe-ZSM-5.