Abstract

This study investigates the production of hydrogen from the electrochemical reforming of short-chain alcohols (methanol, ethanol, iso-propanol) and their mixtures. High surface gas diffusion Pt/C electrodes were interfaced to a Nafion polymeric membrane. The assembly separated the two chambers of an electrochemical reactor, which were filled with anolyte (alcohol + H2O or alcohol + H2SO4) and catholyte (H2SO4) aqueous solutions. The half-reactions, which take place upon polarization, are the alcohol electrooxidation and the hydrogen evolution reaction at the anode and cathode, respectively. A standard Ag/AgCl reference electrode was introduced for monitoring the individual anodic and cathodic overpotentials. Our results show that roughly 75% of the total potential losses are due to sluggish kinetics of the alcohol electrooxidation reaction. Anodic overpotential becomes larger as the number of C-atoms in the alcohol increases, while a slight dependence on the pH was observed upon changing the acidity of the anolyte solution. In the case of alcohol mixtures, it is the largest alcohol that dictates the overall cell performance.

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