Alkali Metal Cation–Sulfate Anion Ion Pairs Promoted the Cleavage of C–C Bond During Ethanol Electrooxidation

Direct ethanol fuel cells show great promise as a means of converting biomass ethanol derived from biomass into electricity. However, the efficiency of complete conversion is hindered by the low selectivity in breaking the C–C bond. This selectivity is determined by factors such as the material structure and reaction conditions, including the nature of the supporting electrolyte. Cations serve not only as facilitators of electricity conduction through ion migration but also as influencers of the reaction pathways. In this study, we utilized differential electrochemical mass spectrometry to track the in situ generation of CO2 during potential scanning. The presence of alkali cations led to an enhancement in the CO2 selectivity. In addition, in situ Raman spectroscopy provided evidence of the formation of alkali metal cation–sulfate anion ion pairs. The catalytic activity and CO2 selectivity were found to be directly correlated to the ionic strength of these ion pairs.