Effective coordination as a predictor of adsorption energies: A model study of NO on Rh(100) and Rh/MgO(100) surfaces

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Materials, Ab Initio Calculations Of Adsorbate Structure And Reactions, Surfaces, Transition Metals And Alloys

Scientific paper

We have studied the adsorption of NO, and the coadsorption of N and O, on four physical and hypothetical systems: unstrained and strained Rh(100) surfaces and monolayers of Rh atoms on strained and unstrained MgO(100) surfaces. We find that as we go from Rh(100) to Rh/Mg0(100), via the other two hypothetical systems, the effective coordination progressively decreases, the d band narrows and its center shifts closer to the Fermi level, and the strength of adsorption and coadsorption increases. Both the strain and the presence of the oxide substrate contribute significantly to this. However, charge transfer is found to play a negligible role due to a canceling out between donation and back-donation processes. Our results suggest that lowering the effective coordination of Rh catalysts by strain, roughening, or the use of inert substrates might lower activation energies for the dissociation of NO.

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