Electronic Structure Origins of CO2 Activation at ZrO2–Cu Boundaries

Abstract

 Electronic interactions at oxide–metal interfaces govern the activation of small molecules. In this study, projected density of states and Bader charge analyses were employed to investigate charge redistribution at ZrO2–Cu interfaces. The results indicate electron transfer from Cu to interfacial Zr atoms, generating partially reduced Zr³⁺ species that strongly interact with CO2. CO2 adsorption energies increase by 0.30–0.45 eV relative to Cu, accompanied by pronounced molecular bending. Linear correlations between interfacial charge accumulation and CO2 activation barriers reveal that electronic tuning at the interface directly controls catalytic performance. These electronic effects translate into a calculated 4.0-fold enhancement in methanol turnover frequency. The study establishes a clear electronic descriptor linking interface structure to activity.