Probing the Dynamics of Low-Overpotential CO 2 -to-CO Activation on Copper Electrodes with Time-Resolved Raman Spectroscopy.

Oxide-derived copper electrodes have displayed a boost in activity and selectivity toward valuable base chemicals in the electrochemical carbon dioxide reduction reaction (CO2RR), but the exact interplay between the dynamic restructuring of copper oxide electrodes and their activity and selectivity is not fully understood. In this work, we have utilized time-resolved surface-enhanced Raman spectroscopy (TR-SERS) to study the dynamic restructuring of the copper (oxide) electrode surface and the adsorption of reaction intermediates during cyclic voltammetry (CV) and pulsed electrolysis (PE). By coupling the electrochemical data to the spectral features in TR-SERS, we study the dynamic activation of and reactions on the electrode surface and find that CO 2 is already activated to carbon monoxide (CO) during PE (10% Faradaic efficiency, 1% under static applied potential) at low overpotentials (-0.35 V RHE ). PE at varying cathodic bias on different timescales revealed that stochastic CO is dominant directly after the cathodic bias onset, whereas no CO intermediates were observed after prolonged application of low overpotentials. An increase in cathodic bias (-0.55 V RHE ) resulted in the formation of static adsorbed CO intermediates, while the overall contribution of stochastic CO decreased. We attribute the low-overpotential CO 2 -to-CO activation to a combination of selective Cu(111) facet exposure, partially oxidized surfaces during PE, and the formation of copper-carbonate-hydroxide complex intermediates during the anodic pulses. This work sheds light on the restructuring of oxide-derived copper electrodes and low-overpotential CO formation and highlights the power of the combination of electrochemistry and time-resolved vibrational spectroscopy to elucidate CO2RR mechanisms.