Investigation of the Ethanol Electro‐Oxidation in Alkaline Membrane Electrode Assembly by Differential Electrochemical Mass Spectrometry

The fuel cell differential electrochemical mass spectrometry (FC‐DEMS) measurements were performed for studying the ethanol oxidation reaction (EOR), using alkaline membrane electrode assemblies (MEAs) made up of nanoparticle Pt catalyst and alkaline polymeric membranes. The obtained results indicate that in an alkaline medium, ethanol undergoes significantly more complete electro‐oxidation to CO₂ than in an acidic MEA using the same Pt anode. The CO₂ current efficiency (CCE) can be compared for acidic and alkaline MEA with similar electrochemical active area on the anode side. The CCE estimated, in case of alkaline MEA with Pt anode, is around 55% at 0.8 V/RHE, 60 °C and 0.1 M ethanol. In comparison, under similar conditions, acidic MEAs using the same anode catalyst show only 2% CCE. This might indicate that the C–C bond scission rates are much higher in alkaline media. However, the mechanism of ethanol oxidation in alkaline media is not exactly known. CO₂ produced in electrochemical reaction forms soluble carbonates in the presence of aqueous alkaline electrolyte. This makes it difficult to study ethanol oxidation in alkaline media using FTIR or model DEMS systems. The alkaline polymer electrolyte membranes as used in this study for making alkaline MEAs provide an important opportunity to observe CO₂ produced during EOR using FC‐DEMS system.