Abstract
The electrooxidation of ethylene glycol (EG) has been studied either in situ on a smooth Pd electrode by FTIR spectroscopy or on nanostructured Pd‐based catalysts by cyclic voltammetry. The electrooxidation on the Pd electrode is dramatically influenced by the pH. Below pH 12, CO~2~ is formed and detected in the thin layer by FTIR, while at higher pH values glycolate, carbonate and oxalate are formed almost simultaneously at a potential of ca. 0.4 V versus RHE. Above 0.9 V glycolate is oxidised to oxalate and carbonate. The nanostructured electrocatalysts Pd–(Ni–Zn)/C, Pd–(Ni–Zn–P)/C and Pd/C are much more active than the smooth Pd electrode (up to 3,300 A g(Pd)^–1^) and give different distributions of the oxidation products. Pd/C is the most selective catalyst yielding glycolate, while mixtures of glycolate (major>60%), oxalate and carbonate are obtained with Pd–(Ni–Zn)/C or Pd–(Ni–Zn–P)/C. Carbonate is produced by oxidation of both glycolate (major contribution) and oxalate, while the major part of oxalate seems to be produced by the direct oxidation of EG.