A comparative computational study on hydrogen adsorption on the Ag(+), Cu(+), Mg(2+), Cd(2+), and Zn(2+) cationic sites in zeolites.

In this article the interaction between H2 and Ag(+), Cu(+), Mg(2+), Cd(2+), and Zn(2+) cations in cluster models of several sizes has been studied computationally. Depending on the changes imposed by the adsorption process on the H2 molecule the activation can vary in a wide range - from only slight weakening of the H-H bond to complete dissociation of the H2 molecule. The NOCV (Natural Orbitals for Chemical Valence) analysis allowed for decomposition of the electron density distortion into contributions easier for interpretation. Three essential factors have been identified (i-iii). In the case of bare cations the main contribution is a donation from σH2 to the cation (i). When a zeolite framework surrounding the cation is introduced, it hinders σ-donation and enhances π-backdonation from the cation to the antibonding orbital of the molecule (ii). For Cu(i) and Ag(i) sites π-backdonation becomes dominant, while for Mg(ii), Cd(ii), and Zn(ii) cations, the σ-donation, albeit diminished, still remains a dominant contribution. Calculations showed that the localization and coordination of Zn(ii) have crucial influence on its interaction with H2. We identified a Zn(2+) position at which the H2 molecule dissociates - here the interaction between H2 and oxygen framework (iii) plays a crucial role. Based on the calculations the mechanism of H2 transformation has been proposed. Upon heterolytic dissociation of H2 the Zn(0) moiety and two OH groups can be formed. Eventually, in two elementary steps, the H2 molecule can be restored. In this case, the ability of the site to activate/dissociate hydrogen is caused by the low coordination number of the zinc cation and the geometry of the site which allows positively charged H2 to interact with framework oxygen what enhances the formation of OH and Z-O-(ZnH)(+) groups.