Theoretical investigation on the reaction mechanism of N2O + CO catalyzed by Ir+ and Co+

The catalysis of N2O + CO is an important reaction system for understanding the performance of catalysts, and can serve as a prototype to investigate a variety of reaction mechanisms of catalytic processes. The reaction of N2O + CO catalyzed by Ir+ and Co+ was studied by using density functional theory (B3LYP). A large basis set of 6-311++G** was used for H, C, N, O and Co atoms, and the effective core potentials (ECPs) of Hay and Wadt with a double-zeta basis set (LanL2DZ) was employed to describe Ir atom. On the basis of full optimization, the reaction mechanism was elucidated with vibrational analysis, and a new process of CO seizing the O atom directly, which has relatively low energy barrier, was reported: the reaction mechanism of N2O to N-2 catalyzed by Co+ is very similar to that of Ir+, but in the quintet reaction pathways of CoO+ + CO to Co+ + CO2, there is only a CO-capture channel. (C) 2010 Elsevier B.V. All rights reserved.