Publication date: 15th December 2025
Glycerol electro‑oxidation offers an attractive route to make use of the surplus generated during biodiesel production while simultaneously yielding valuable organic acids and hydrogen.[1] Xylitol, another bio‑derived polyol with potential for producing commodity chemicals, has received less scientific attention than glycerol. However, the extensive research on glycerol provides a solid basis for examining the reaction mechanisms of xylitol and for identifying differences due to variations in molecular size.
Here, we investigated the electrochemical oxidation of glycerol, erythritol and xylitol on Pt and Ag in a MEA-type flow cell. For better comparison, all measurements were terminated after 360 C had passed. Product formation was monitored by liquid chromatography and NMR spectroscopy. On Pt, the polyols are first oxidised to their respective aldehydes on the electrode surface. The subsequent reactions are dominated by the C-C bond cleavage behaviour of the aldehyde under the alkaline reaction conditions. While glyceraldehyde forms mainly C3 carboxylic acid, erythrose and xylose mainly decompose to various C1-C3 acids and form oligomeric compounds. On Ag, only glyceric-, glycolic-, and formic acid are formed from all three polyols. For the oxidation of glycerol on Ag, computational and experimental results indicate the formation of glycolaldehyde and formic acid.[2,3] A similar cleavage behaviour to an acid and an aldehyde is assumed for erythritol and xylitol, and is reflected in the product outcome.
These results provide insights into the influence of polyol length on the distribution of the electrochemical oxidation products.
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