Lowering Effective Coordination Promotes Adsorption of NO on Rh(100) and Rh/MgO(100)surfaces

TL;DR

This study demonstrates that reducing the effective coordination of Rh surfaces, through strain or substrate effects, enhances NO adsorption, potentially improving catalytic reduction of NO to N2.

Contribution

It reveals how lowering effective coordination via strain and oxide substrates increases NO adsorption on Rh surfaces, with minimal charge-transfer effects.

Findings

Decreased effective coordination leads to stronger NO adsorption.

Strain and oxide substrates significantly influence adsorption strength.

Charge-transfer effects are negligible due to cancellation between donation and back-donation.

Abstract

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 co-adsorption increases. Both 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 cancelling out between donation and back-donation processes. Our results suggest that lowering effective coordination of Rh catalysts by strain, roughening or the use of inert substrates might improve reaction rates for the reduction of NO to N$_2$.