New aspects of operando Raman spectroscopy applied to electrochemical CO2 reduction on Cu foams

The mechanism of electrochemical CO2 reduction (CO2RR) on copper surfaces is still insufficiently understood. Operando Raman spectroscopy is ideally suited to elucidate the role of adsorbed reaction intermediates and products. For a Cu foam material which has been previously characterized regarding electrochemical properties and product spectrum, 129 operando spectra are reported, covering the spectral range from 250 to 3300 cm−1. (1) The dendritic foam structure facilitates surface-enhanced Raman spectroscopy (SERS) and thus electrochemical operando spectroscopy, without any further surface manipulations. (2) Both Raman enhancement and SERS background depend strongly on the electric potential and the “history” of preceding potential sequences. (3) To restore the plausible intensity dependencies of Raman bands, normalization to the SERS background intensity is proposed. (4) Two distinct types of *CO adsorption modes are resolved. (5) Hysteresis in the potential-dependent *CO desorption supports previous e...