The electrochemical reduction of CO2 (CO2RR) to multi-carbon products such as ethanol (C2H5OH) and ethylene (C2H4) is a promising strategy for mitigating CO2 emissions and producing valuable chemicals. In this study, we investigate the role of ZnO in enhancing the performance of Cu-based catalysts for CO2RR. Using both experimental and theoretical approaches, we demonstrate that ZnO incorporation significantly improves the catalytic efficiency of Cu by modifying its electronic structure, stabilizing key intermediates, and facilitating C–C coupling. DFT calculations show that ZnO stabilizes intermediates such as *CO and *HCOH, promoting their hydrogenation and enhancing C2 product formation. The presence of oxygen vacancies (OVs) on the Cu-ZnO interface is found to facilitate proton-coupled electron transfer (PCET) and H-spillover, leading to improved catalytic performance. XPS and UV–Vis DRS analyses confirm that ZnO modifies the Cu surface, increasing the Cu0/Cu+ species and narrowing the band gap, which enhances charge transfer and intermediate stabilization. The CZ catalyst exhibits significantly higher Faradaic efficiency for C2 products compared to the Cu catalyst, as confirmed by experimental data. These findings highlight the importance of defect engineering in the design of more efficient catalysts for CO2 reduction. This study provides valuable insights into optimizing Cu-based catalysts for sustainable CO2 utilization and C2 product formation.
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