Investigating the Electrochemical CO2 Reduction Mechanism on Oxide-Derived Copper Using in Situ FTIR Spectroscopy

Abstract

Oxide-derived copper (OD-Cu) electrocatalysts have been extensively used for CO2 reduction reaction (CO2RR) applications in recent years due to their capability to selectively produce valuable C2 compounds. The mechanism of CO2 reduction on these surfaces, however, is still not clearly understood. Using in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS), we show how the copper pre-oxidation process can significantly influence the adsorption of various CO2RR intermediates. Upon mildly anodizing a Cu thin film, we observed a redshift on the *CO2 – band, indicating that the initial CO2 adsorption and activation step is promoted on the oxide-derived surface. Additionally, we observed a faster growth of the *COatop band for the anodized copper film at low overpotentials, which demonstrates how a high *CO coverage can be achieved on OD-Cu. Finally, for the first time, we observed the simultaneous formation of two bands at 1327 cm–1 and 1425 cm–1 on the anodized Cu thin film. Using DFT calculations, we show that these bands match the theoretical vibrational frequencies of the *COCHO dimer, a key intermediate of the C2 pathway. Furthermore, our calculations show that the thermodynamics of *CO and *CHO coupling can be improved in the presence of the subsurface oxygen sites in OD-Cu. Our findings reveal the different aspects through which the CO2 reduction mechanism can be improved on OD-Cu electrocatalysts as compared to metallic copper.This work was financially supported by the Research Grants Council (16310419, 16309418, and 16304821) and the Innovation and Technology Commission (grant no. ITC-CNERC14EG03).