Nature of the metal-support interaction in bifunctional catalytic Pt/H-ZSM-5 zeolite.

The metal-support interaction of a dispersed Pt atom on H-ZSM-5 zeolite has been investigated by using an embedded cluster and cluster models with the density functional theory/B3LYP functional method. We found that the Pt atom interacts with a Brønsted proton and a nearby framework oxygen. Interaction with the framework oxygen causes electron transfer from the zeolite to the Pt atom. Concurrently, a Brønsted proton stabilizes the Pt atom on the zeolite surface by withdrawing excess electron density from the Pt atom. These charge transfers result in a zero net charge on the Pt atom while changing its orbital occupation. The binding energy of Pt on the Brønsted acid was 15 kcal/mol. Inclusion of the Madelung potential by Surface Charge Representation of the Electrostatic Embedded Potential method (SCREEP) had small effects on structure and charge density of Pt/H-ZSM-5 but it shifted the stretching mode of CO toward a higher frequency by almost 40 cm(-1). The frequency shift of absorbed CO calculated with embedded cluster models was from 8 to 11 cm(-1) red shift, compared to 20 cm(-1) red shift from experiment. This implies that not only the electronic state of the Pt atom but also the Madelung potential of the support is responsible for the observed small red shift of CO on the Pt-H-ZSM-5.