Modeling of Substitutional Defects in Magnesium Dichloride Polymerization Catalyst Support

We evaluate methods and models for the periodic quantum chemical treatment of defects in MgCl2 polymerization catalyst support and demonstrate the applicability of the approach for a study of chemical substitution of chlorine with bromine. Effects of the defects are evaluated through binding of methanol to catalytically relevant MgCl2 surfaces. Our results show that the hybrid density functional PBEO method reproduces the MgCl2 crystal structure in good agreement with experiments and that a triple-zeta quality basis set is required to evaluate the donor binding properties. Furthermore, the effects of the defects depend on their position in the crystal lattice, and destabilization of the crystal lattice results in increased donor binding energy. Therefore, substitutions at the coordinatively unsaturated edges typically stabilize the crystallites and lower the donor binding energies, whereas substitutions at the coordinatively saturated bulk typically destabilize the crystallites and increase the donor binding energies. The effects are stronger on the (104) than on the (110) surface. The study is readily extendable to other kinds of defects occurring in crystallites.