Unveiling the Cation Effects on Electrocatalytic CO₂ Reduction via Operando Surface-enhanced Raman Spectroscopy

The electrocatalytic carbon dioxide reduction reaction (CO₂RR) can be significantly improved by the presence of alkali metal cations, yet the underlying mechanisms remain unclear. In this study, we developed clean Cu nanoparticles with tailored curvatures to modulate the local concentration of K⁺ cations and investigate their effects on CO₂RR. The adjustment of particle curvature allows for direct control over cation concentrations within the electrochemical double layer, enabling broad-range modulation of cation concentration without concerns regarding solubility limitations or anionic interference. By tuning the plasmonic modes of the Cu particles, we achieved highly sensitive surface-enhanced Raman spectroscopy (SERS) under resonant conditions, facilitating in situ tracking of the short-lived intermediates in CO₂RR. Our results revealed that K⁺ cations not only stabilize *COOH and *CO species and reduce the reaction energy barrier for C─C coupling but also increase the surface coverage of *CO, particularly for bridge *CO configurations. Furthermore, our findings suggest that the interactions between bridge *CO and atop *CO play a crucial role in facilitating the C─C coupling, offering insights for the design of electrocatalysts for CO₂RR.