Spectroelectrochemical Exploration of Biogenic Substrates for Electrosynthesis

Abstract

AbstractSpectroelectrochemistry, especially ATR‐SEIRAS, is an emerging method to identify key descriptors for optimizing reaction systems in organic electrosynthesis. Here, the upgrading of biogenic acids via Kolbe electrolysis and reductive transformations was studied. The findings affirm acid group adsorption on electrodes, consistent with existing literature. The effectiveness of Kolbe reaction in suppressing the parasitic ethanol oxidation reaction was observed, whereas it faces stiff competition from the methanol oxidation reaction. Parallel reduction and reductive amination of levulinic acid were uncovered, both relying on adsorbed organic species rather than molecular H2. Intriguingly, the electrode's polarization influences the bond strength, enabling discrimination between acid and ketone species within levulinic acid.