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

• Published in: Journal of molecular modeling 2022-12, Vol.28 (12), p.394-394, Article 394
• Main Authors: Prates, Letícia M., De M. Carneiro, José W., De M. Cruz, Maurício T.
• Format: Article
• Language: English
• Subjects: Adsorption; Aluminum oxide; Characterization and Evaluation of Materials; Charge transfer; Chemistry; Chemistry and Materials Science; Computer Appl. in Life Sciences; Computer Applications in Chemistry; Density functional theory; Molecular Medicine; Molecular orbitals; Nucleation; Original Paper; Palladium; Synergistic effect; Theoretical and Computational Chemistry; Transitional aluminas
• ISSN: 1610-2940; 0948-5023
• DOI: 10.1007/s00894-022-05374-7

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 /γ-alumina (110D) model (Pd 4 /Al 13 O 23 H 7 ). Our results indicate the occurrence of an electronic metal − support interaction (EMSI) which induces a most intense charge transfer in the Pd 4  → γ-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  →  2π * ) backdonation (bridge mode). Graphical Abstract MSI and MMI effects on the nature of the Pd − O (electrostatic) and Pd − Al (covalent) bonds, charge transfer into Pd 4 /γ-Al 2 O 3 (110D) interface (back donation) and preferential site for adsorption of a single NO molecule and an additional Pd atom (Pd − O).