The electrochemical behavior of ethanol and acetaldehyde was studied at rhodium electrodes in acid solutions using electrochemical mass spectrometry (DEMS). Acetaldehyde and CO 2 were detected from bulk ethanol, whereas only CO 2 was recorded from acetaldehyde. The production of acetic acid could not be confirmed with this method. The formation of methane was established from both molecules, which suggests that the fragmentation of the C−C chain occurs during the electroreduction and/or adsorption processes. Adsorbed species were isolated by applying a flow cell procedure. The residues produce CO 2 and methane during oxidation and reduction reactions, respectively, the amount of these compounds depending on the adsorption potential. By use of isotopic labeled 12 CH 3 13 CH 2 OH and 12 CH 3 13 CHO, the contribution of each C atom in the adsorbate was distinguished. It was established that the CH 3 group oxidizes at potentials within the O adsorption potential region of rhodium during the positive-going sweep and also at E < 0.60 V during the reverse scan. The CH 2 OH or CHO groups yield CO 2 in the same potential region as CO ad . The influence of the anion on these reactions was established using sulfuric and perchloric acids as base electrolytes, being noticeable for ethanol adsorption. Compared to Pt, Rh electrodes exhibit an enhanced activity for deprotonation and C−C cleavage reactions.
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Méndez et al. (2002) studied this question.
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