Mechanistic effects of blending formic acid with ethanol on Pd activity towards formic acid oxidation in acidic media

The direct formic acid fuel cell (DFAFC) is one of the most promising direct liquid fuel cells. Pd is the most active catalyst towards formic oxidation, however, it suffers from CO-like poisoning and instability in acidic media. Blending formic acid with ethanol is known to synergistically enhance the Pt catalytic activity of Pt. However, it has not been studied in the case of Pd. In this study, ethanol/formic acid blends were tested, aiming at understanding the effect of ethanol on the formic acid oxidation mechanism at Pd and how the direct and indirect pathways could be affected. The blends consisted of different formic acid (up to 4 M) and ethanol (up to 0.5 M) concentrations. The catalytic activity of a 40% Pd/C catalyst was tested in 0.1 M H₂SO₄ + XFA + YEtOH using cyclic voltammetry, while the catalyst resistance to poisoning in the presence and absence of ethanol was tested using chronopotentiometry. The use of these blends is found to not only eliminate the indirect pathway but also slowly decrease the direct pathway activity too. That is believed to be due to the different ethanol adsorption orientations at different potentials. This study should open the door for further studying the oxidation of FA/ethanol blends using different pHs and different Pd-based catalysts.