Physics

Electrode

Surface-enhanced Raman spectroscopy

Copper

Analytical Chemistry (journal)

Optics

Catalysis

Raman scattering

Physical chemistry

Inorganic chemistry

Chemistry

Metallurgy

Materials science

Ethylene

Raman spectroscopy

Chromatography

Electrochemistry

Biochemistry

Angewandte Chemie International Edition

The electrocatalytic carbon dioxide (CO 2 ) reduction reaction (CO 2 RR) into hydrocarbons is a promising approach for greenhouse gas mitigation, but many details of this dynamic reaction remain elusive. Here, time‐resolved surface‐enhanced Raman spectroscopy (TR‐SERS) is employed to successfully monitor the dynamics of CO 2 RR intermediates and Cu surfaces with sub‐second time resolution. Anodic treatment at 1.55 V vs. RHE and subsequent surface oxide reduction (below −0.4 V vs. RHE) induced roughening of the Cu electrode surface, which resulted in hotspots for TR‐SERS, enhanced time resolution (down to ≈0.7 s) and fourfold improved CO 2 RR efficiency toward ethylene. With TR‐SERS, the initial restructuring of the Cu surface was followed (&lt;7 s), after which a stable surface surrounded by increased local alkalinity was formed. Our measurements revealed that a highly dynamic CO intermediate, with a characteristic vibration below 2060 cm −1 , is related to C−C coupling and ethylene production (−0.9 V vs. RHE), whereas lower cathodic bias (−0.7 V vs. RHE) resulted in gaseous CO production from isolated and static CO surface species with a distinct vibration at 2092 cm −1 .

Sub‐Second Time‐Resolved Surface‐Enhanced Raman Spectroscopy Reveals Dynamic CO Intermediates during Electrochemical CO<sub>2</sub> Reduction on Copper

Sub‐Second Time‐Resolved Surface‐Enhanced Raman Spectroscopy Reveals Dynamic CO Intermediates during Electrochemical CO2 Reduction on Copper

Sub‐Second Time‐Resolved Surface‐Enhanced Raman Spectroscopy Reveals Dynamic CO Intermediates during Electrochemical CO₂ Reduction on Copper