Influence of a Cu-zirconia interface structure on CO₂ adsorption and activation

CO₂ adsorption and activation on a catalyst are key elementary steps for CO₂ conversion to various valuable products. In the present computational study, we screened different Cu-ZrO₂ interface structures and analyzed the influence of the interface structure on CO₂ binding strength using density functional theory calculations. Our results demonstrate that a Cu nanorod favors one position on both tetragonal and monoclinic ZrO₂ surfaces, where the bottom Cu atoms are placed close to the lattice oxygens. In agreement with previous calculations, we find that CO₂ prefers a bent bidentate configuration at the Cu-ZrO₂ interface and the molecule is clearly activated being negatively charged. Straining of the Cu nanorod influences CO₂ adsorption energy but does not change the preferred nanorod position on zirconia. Altogether, our results highlight that CO₂ adsorption and activation depend sensitively on the chemical composition and atomic structure of the interface used in the calculations. This structure sensitivity may potentially impact further catalytic steps and the overall computed reactivity profile.