Effect of Surface Site on the Spin State for the Interaction of NO with Pd2, Rh2 and PdRh Nanoparticles Supported at Regular and Defective MgO001 SurfacesReport as inadecuate




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An attempt has been made to analyze the effect of surface site on the spin state for the interaction of NO with Pd2, Rh2 and PdRh nanoparticles that supported at regular and defective MgO001 surfaces. The adsorption properties of NO on homonuclear, Pd2, Rh2, and heteronuclear transition metal dimers, PdRh, that deposited on MgO001 surface have been studied by means of hybrid density functional theory calculations and embedded cluster model. The most stable NO chemisorption geometry is in a bridge position on Pd2 and a top configuration of Rh2 and PdRh with N-down oriented. NO prefers binding to Rh site when both Rh and Pd atoms co-exist in the PdRh. The natural bond orbital analysis NBO reveals that the electronic structure of the adsorbed metal represents a qualitative change with respect to that of the free metal. The adsorption properties of NO have been analyzed with reference to the NBO, charge transfer, band gaps, pairwise and non-pairwise additivity. The binding of NO precursor is dominated by the EiMx-NO pairwise additive components and the role of the support was not restricted to supporting the metal. The adsorbed dimers on the MgO surface lose most of the metal-metal interaction due to the relatively strong bond with the substrate. Spin polarized calculations were performed and the results concern the systems in their more stable spin states. Spin quenching occurs for Rh atom, Pd2, Rh2 and PdRh complexes at the terrace and defective surfaces. The adsorption energies of the low spin states of spin quenched complexes are always greater than those of the high spin states. The metal-support and dimer-support interactions stabilize the low spin states of the adsorbed metals with respect to the isolated metals and dimers. Although the interaction of Pd, Rh, Pd2, Rh2 and PdRh particles with Fs sites is much stronger than the regular sites O2-, the adsorption of NO is stronger when the particular dimers are supported on an anionic site than on an Fs site of the MgO001. The encountered variations in magnetic properties of the adsorbed species at MgO001 surface are correlated with the energy gaps of the frontier orbitals. The results show that the spin state of adsorbed metal atoms on oxide supports and the role of precursor molecules on the magnetic and binding properties of complexes need to be explicitly taken into account.

KEYWORDS

Surface Reactions, NO, Bimetallic Nanoparticles, Spin State and Charge Transfer

Cite this paper

Aal, S. 2016 Effect of Surface Site on the Spin State for the Interaction of NO with Pd2, Rh2 and PdRh Nanoparticles Supported at Regular and Defective MgO001 Surfaces. Open Journal of Physical Chemistry, 6, 1-20. doi: 10.4236-ojpc.2016.61001.





Author: S. Abdel Aal

Source: http://www.scirp.org/



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