Membrane-less ethanol electrooxidation over pd-m (M: Sn, mo and re) bimetallic catalysts

Abstract

The effect of the addition of three oxophilic co-metals (Sn, Mo and Re) on the electrochemical performance of Pd in the ethanol oxidation reaction (EOR) was investigated by performing half-cell and membrane-less electrolysis cell experiments. While the additions of Sn and Re were found to improve significantly the EOR performance of Pd, Mo produced no significant promotional effect. When added in significant amounts (50:50 ratio), Sn and Re produced a 3–4 fold increase in the mass-normalized oxidation peak current as compared to the monometallic Pd/C material. Both the electrochemical surface area and the onset potential also improved upon addition of Sn and Re, although this effect was more evident for Sn. Cyclic voltammetry (CV) measurements revealed a higher ability of Sn for accommodating OH- species as compared to Re, which could explain these results. Additional tests were carried out in a membrane-less electrolysis system. Pd50Re50/C and Pd50Sn50/C both showed higher activity than Pd/C in this system. Chronopotentiometric measurements at constant current were carried out to test the stability of both catalysts in the absence of a membrane. Pd50Sn50/C was significantly more stable than Pd50Re50/C, which showed a rapid increase in the potential with time. Despite operating in the absence of a membrane, both catalysts generated a high-purity (e.g., 99.99%) hydrogen stream at high intensities and low voltages. These conditions could lead to significant energy consumption savings compared to commercial water electrolyzers.