Theoretical characterization of zeolite encapsulated platinum clusters in the presence of water molecules

Abstract

Zeolite encapsulated metal clusters have shown high catalytic activity and superior stability due to confinement effects, the synergy between acidic and metal active sites, and strong metal–zeolite interactions. In the present work, density functional theory calculations were employed to study the stability of encapsulated Pt_n (n = 1–6) clusters in the zeolitic frameworks including Silicalite-1 and H-MFI. It has been found that the metal-zeolite interaction becomes stronger with the increasing Pt_n cluster size for both zeolitic frameworks. The encapsulated Pt_n clusters in the vicinity of the Brønsted acid site (BAS) of H-MFI form more stable Pt_nH_x (x = 1, 2) clusters. The presence of water molecules around the encapsulated Pt₆ cluster further enhances its stability, while the oxidation states of the encapsulated Pt_n cluster are largely affected by the BAS site and the surrounding water molecules. As the water concentration increases, water dissociation becomes more facile on the Pt₆@Silicalite-1 cluster while an opposite trend is found over the Pt₆H₂@H-MFI cluster. The proton of the BAS site can be transferred to the encapsulated Pt₆ cluster via a hydronium cluster H⁺(H₂O)_n, leading to the formation of the Pt₆H₂@H-MFI cluster.