Seriatim ECSTM-ECPMIRS of the adsorption of carbon monoxide on Cu(100) in alkaline solution at CO_2-reduction potentials

Abstract

It was recently demonstrated that the sequential or seriatim application of electrochemical scanning tunneling microscopy (ECSTM) and differential electrochemical mass spectrometry (DEMS) enables the correlation, under actual reaction conditions, of a specific structure on a Cu electrode surface with the generation of a particular CO-reduction product. As an extension of the operando hyphenated-technique approach, we paired ECSTM with electrochemical polarization-modulation IR reflection-absorption spectroscopy (ECPMIRS) to identify a delineating potential that affected the coverage, the molecular orientation, and the adlattice structure of CO adsorbed on Cu(100) in 0.1 M KOH under CO_2-reduction conditions. The results may have significant ramifications on the theory-based reaction mechanism for the formation of C_2 compounds, as well as insights into the mode of coordination between CO and zerovalent Cu.