Molecular adsorption and metal-support interaction for transition-metal clusters in zeolites: NO adsorption on Pdn (n=1-6) clusters in mordenite
- Author(s)
- Robert Grybos, Lubomir Benco, Tomas Bucko, Juergen Hafner
- Abstract
The adsorption of NO molecules on Pdnclusters of varying size (n=1–6) located in the main channel of mordenite and the interaction of the metallic clusters with the zeolitic framework were investigated using ab initio density-functional calculations under periodic boundary conditions. The supported clusters are created by binding Pd2+n cations to the inner cavity of a deprotonated Al-exchanged zeolite with an Al/Si ratio of 1/11, such that a charge-neutral system is created. Compared to the highly symmetric structures of the gas-phase clusters, the clusters bound to the zeolitic framework undergo appreciable geometric distortions lowering their symmetry. The distortions are induced by strong interactions with “activated” framework oxygens located close to the charge-compensating Al/Si substitution sites, but the cluster forms also weaker bonds to “nonactivated” oxygen atoms. The interaction with the framework also affects the electronic and magnetic properties of the clusters. While in the gas phase all clusters (except the isolated Pd atom with a closed d10ground state) have a paramagnetic moment of 2μB, in the zeoliteclusters with two to four atoms have zero magnetic moment, while the Pd5cluster has a magnetic moment of 2μB and for the Pd6cluster, it is even enhanced to 4μB (but the magnetic energy differences relative to low-spin configurations are modest). Analysis of the magnetization densities shows that in all clusters with zero total moment (singlet ground state), there are sites with excess spin densities of opposite sign. The influence of the cluster-support interaction on the chemical properties of the clusters has been tested by the adsorption of NO molecules. The results demonstrate the interplay between the molecule-cluster and cluster-framework interactions, which can lead to an increase or decrease in the adsorption energy compared to NO on a gas-phase cluster. While on the gas-phase clusteradsorption in low-coordination sites (vertex or bridge) is preferred, for the cluster in the zeoliteadsorption in threefold coordinated hollow or twofold bridge sites is preferred. The magnetic properties of the clusters and of the paramagnetic NO molecule play an important role. For the supported clusters with zero magnetic moment, upon adsorption the spin of the molecule is transferred to the cluster (and induces also a modest polarization of the framework). For magnetic clusters, spin pairing induces a reduced magnetic moment of the NO-Pdn complex. The redshift of the NO stretching frequencies is reduced compared to the free clusters by the cluster-support interaction for the smaller clusters, while it remains essentially unchanged for the larger clusters. A detailed electronic analysis of the cluster-support interactions and of the adsorption properties is presented.
- Organisation(s)
- Computational Materials Physics
- External organisation(s)
- Polish Academy of Sciences (PAS)
- Journal
- Journal of Chemical Physics
- Volume
- 130
- No. of pages
- 20
- ISSN
- 0021-9606
- DOI
- https://doi.org/10.1063/1.3079542
- Publication date
- 2009
- Peer reviewed
- Yes
- Austrian Fields of Science 2012
- 103009 Solid state physics, 103015 Condensed matter, 103025 Quantum mechanics, 103036 Theoretical physics
- Portal url
- https://ucris.univie.ac.at/portal/en/publications/molecular-adsorption-and-metalsupport-interaction-for-transitionmetal-clusters-in-zeolites-no-adsorption-on-pdn-n16-clusters-in-mordenite(cc597fdd-29c6-4e60-b53e-634a41f5cf6a).html