Cobalt-exchanged ferrierite is a selective catalyst for the reduction of nitrogen oxides in the presence of
oxygen. The activity of each isolated cobalt cation has been suggested to depend on the local zeolite
environment. Two of the three cobalt extraframework sites proposed in the literature were investigated with
density functional theory calculations. The electronic structure, geometry, and infrared spectra of eight clusters
were calculated and compared to experiment. Exchanged cobalt cations were most stable in the high-spin
electronic configuration. The stability of cobalt in each site was evaluated by calculating the cobalt−zeolite
binding energy. The calculations also show the important role of zeolite aluminum location in extraframework
cobalt siting. Only one of the eight clusters was able to reproduce all of the experimental characteristics of
the predominant cobalt species. A secondary cobalt species was predicted to most likely correspond to one
of four possible candidate clusters.