Copper-Modified Zinc-Based Perovskite for Electrochemical Reduction of CO₂ to CO: The Role of Copper Loading and Perovskite Reconstruction

The electrochemical reduction of carbon dioxide (eCO2RR) has emerged as a promising strategy for mitigating atmospheric CO2 levels and producing value-added chemicals. In this study, we report the development of a perovskite-derived 10 wt % Cu–LZO electrocatalyst that demonstrates exceptional performance in eCO2RR. This catalyst achieves a high Faradaic efficiency of 91% for CO production at a moderate overpotential of −1.1 V vs reversible hydrogen electrode (RHE), alongside a remarkable current density of −46.5 mA mg–1 and stable performance over 30 h. Structural characterizations, including X-ray diffraction and transmission electron microscopy, reveal the successful incorporation of Cu domains on the LZO surface, forming abundant Cu–LZO interfaces. X-ray photoelectron spectroscopy (XPS) and in situ infrared spectroscopy further elucidate the enhanced electron transfer and stable adsorption of *COOH intermediates at the interface, which are critical for improved CO selectivity. Compared to the physical mixtures of Cu and LZO, the interfacial structure in the loaded catalyst plays a pivotal role in boosting electrocatalytic activity. Additionally, the carbonate layer formed during eCO2RR enhances catalyst stability by retarding surface reconstruction. Our work not only introduces an efficient perovskite catalyst for eCO2RR but also highlights the importance of interfacial engineering in advancing electrochemical reactions.