Defect-Driven CO₂ Activation at Oxygen-Deficient ZrO₂–Cu Interfaces

Abstract

Defects in oxide components often play a decisive role in catalytic activity. In this study, oxygen vacancies were systematically introduced into ZrO2 clusters supported on Cu to evaluate their effect on CO2 hydrogenation. Vacancy formation enhances local charge localization and strengthens CO2 adsorption by up to 0.44 eV. Microkinetic analysis shows that moderate vacancy concentrations (3–6%) maximize methanol selectivity, whereas higher defect densities favor CO formation. These results demonstrate how controlled defect engineering can fine-tune inverse catalyst performance.