Influence of the metal - support and metal - metal interactions on Pd nucleation and NO adsorption in a Pd4/γ-Al2O3 (110D) model

The role played by the metal - support (MSI) and metal - metal (MMI) interactions on two important processes in controlling the catalyst performance - nucleation and molecular adsorption - has been investigated using density functional theory (DFT), by means of B3LYP functional, combined with localized molecular orbital energy decomposition analysis (LMOEDA), and natural bond orbital (NBO) calculations, with aid of a Pd-4/gamma-alumina (110D) model (Pd-4/Al13O23H7). Our results indicate the occurrence of an electronic metal - support interaction (EMSI) which induces a most intense charge transfer in the Pd-4 -> gamma-alumina backdonation direction, most expressive in Pd -> Al, promoting an electronic redistribution within the units and attenuating the MMI. Nevertheless, the MSI/MMI synergistic effect seems to favor slightly the nucleation of a fifth palladium atom, leading to a distorted square pyramidal arrangement for Pd-5. The LMOEDA analysis points to a mostly covalent character in the Pd - Al bonds, whereas the Pd - O bonds are mainly electrostatic in nature. The palladium atoms deposited on oxygen anions are the acid centers, where both NO molecule and an additional palladium atom anchor more strongly. In addition, the MSI/MMI effect, through the electronic and geometric contributions, drives the adsorption of the NO molecule to the mode which most favors the Pd -> NO (4d(z)(2) -> 2 pi*) backdonation (bridge mode).

Automated summary

The study investigates the effects of metal-support and metal-metal interactions on catalyst performance using density functional theory. The results demonstrate the occurrence of electronic metal-support interaction, which promotes charge transfer and electronic redistribution, weakening the metal-metal interaction. Additionally, the interaction favors nucleation of a fifth palladium atom and molecular adsorption.