First Principles Study of Carbon Monoxide Adsorption on Zirconia-Supported Copper

TL;DR

This study uses first principles calculations to analyze how carbon monoxide adsorbs on copper supported on zirconia surfaces, revealing preferred binding sites and comparing stability with other copper surfaces.

Contribution

It provides detailed insights into CO adsorption energies and sites on zirconia-supported copper, a novel investigation combining surface structure analysis with adsorption energetics.

Findings

CO binds atop terminal oxygen on zirconia-supported copper

Adsorption energy on supported copper is over 0.2 eV more stable than on bare copper

Preferred binding site is atop the terminal oxygen atom

Abstract

We have calculated the adsorption energy of carbon monoxide on a monolayer of copper adsorbed on the (111) face of cubic zirconia. We investigate the structural parameters of three phases of bulk zirconia (cubic, tetragonal, and monoclinic) and find excellent agreement with experiment. We have also analyzed the structural relaxation of both the stoichiometric and reduced (111) surfaces of cubic zirconia ($c$-ZrO$_2$). For adsorption of copper on $c$-ZrO$_2$, we find that the preferred binding site is atop the terminal oxygen atom, favored by 0.3 eV over other high symmetry sites. We compare CO adsorption on zirconia-supported copper to the results of carbon monoxide on copper (100) (S. P. Lewis and A. M. Rappe, J. Chem. Phys. {\bf 110}, 4619,(1999).) and show that adsorption on oxide-supported copper is over 0.2 eV more stable than adsorption on the bare surface.