Small Transition-Metal Mixed Clusters as Activators of the C-O Bond. FeCu-CO (n + m = 6): A Theoretical Approach

Binding of carbon monoxide, CO, and its activation on the surface of the FeCuCO (n + m = 6) clusters are studied in this work. Using the BPW91/6-311 + G(2d) method, we have found that adsorption of the CO molecule on the surface of FeCu (n + m = 6) clusters is thermochemically favorable. Atop and bridge CO cluster coordinations appear for pure, Fe₆ and Cu₆, and mixed, Fe₂Cu₄ and Fe₄Cu₂, clusters. Threefold coordination takes place for Fe₃Cu₃-CO where the CO bond length, d_CO, suffers a largest increase from 1.128 ± 0.014 Å for bare CO up to 1.21 Å. The CO stretching, ν_CO, as an indicator for the CO bond weakening is redshifted, from 2099 ± 4 cm^-1 for isolated CO up to 1690 cm^-1 for Fe₃Cu₃CO and 1678 cm^-1 for Fe₆CO. In addition, in Cu₆CO, the strongest CO bond is slightly weakened as it has a bond length of 1.15 Å and a ν_CO of 2029 cm^-1. There is a correlation between the CO bond weakening and the increase of CO coordination in FeCuCO, which in turns promotes the transference of charges from the metal core into the antibonding orbitals of CO. Substitution of up to three Cu atoms in Fe₆ increases the adsorption energies and the activation of CO. Indeed, FeCu (n + m = 6) are promising clusters to catalyze CO dissociation, particularly Fe₃Cu₃, Fe₅Cu, and Fe₆, which have large CO bond lengths and CO adsorption energies. The Bader analysis of the electronic density indicates that FeCuCO species with threefold coordination show a rise in the C-O covalent character due to the less electronic polarization. They also show important M → CO charge transfer, which favors the weakening of the CO bond.