Insights into the mechanism of electrochemical chloride oxidation in ethanol from X-ray photoelectron spectroscopy, quiescent solution voltammetry, and rotating ring-disk electrodes.

The wide availability of bio-derived alcohols provides the impetus to develop processes that convert them to valuable chemicals. The chloride ion is a redox mediator for electrocatalytic ethanol oxidation to 1,1-diethoxyethane (1,1-DEE) through an ethyl hypochlorite (EtOCl) intermediate, and this paper describes the chloride oxidation reaction (COR) to EtOCl on a glassy carbon (GC) electrode. Voltammetry measurements on a GC electrode in inert acetonitrile solvent combined with  X-ray photoelectron spectroscopy (XPS) establish a Volmer step, where chloride ion from solution chemisorbs and is oxidized.