The electrochemical CO2 reduction reaction (CO2RR) holds tremendous promise as a strategy for lowering atmospheric CO2 levels and creating new clean energy sources. The conversion of CO2RR to CO, in particular, has garnered significant scientific interest due to its industrial feasibility. Within this context, the CuZn-based electrocatalyst presents an attractive alternative to conventional CO-selective electrocatalysts, which are often costly and scarce. Nevertheless, the wide-range utilization of CuZn electrocatalysts requires a more comprehensive understanding of their performance and characteristics. In this study, we synthesized ZnO nanorods through electrodeposition and subsequently coated them with CuxO overlayers prepared by atomic layer deposition (ALD). CuxO significantly enhanced CO selectivity, and 88% CO selectivity at a relatively low potential of -0.8 V was obtained on an optimized CuxO overlayer thickness (CuxO-250/ZnO). The addition of CuxO on ZnO was found to dramatically increase the electrochemical surface area (ESCA), lower the charge-transfer resistance (Rct), and introduce new active sites in the ε-CuZn4 phase. Furthermore, electrochemical Raman spectroscopy results showed that the CuxO-250/ALD electrode developed a ZnO layer on the surface during the CO2RR, while the bare ZnO electrode showed no evidence of ZnO during the reaction. These results suggest that the addition of CuxO by ALD played a crucial role in stabilizing ZnO on the surface. The initial amount of CuxO was shown to further affect the redeposition of the ZnO layer and hence affect the final composition of the surface. We attribute the improvement in CO selectivity to the introduction of both ε-CuZn4 and ZnO that developed during the CO2RR. Overall, our study provides new insights into the dynamic behavior and surface composition of CuZn electrocatalysts during CO2RR.
Keywords: CO selectivity; CO2 reduction; CuZn; atomic layer deposition; galvanic replacement.