Surface (electro-)chemistry on Pt(111) modified by a Pseudomorphic Pd monolayer

The formic acid and methanol oxidation reaction are studied on Pt(111) modified by a pseudomorphic Pd monolayer (denoted hereafter as the Pt(111)-Pd-1 ML System) in 0.1 M HClO4 solution. The results are compared to the bare Pt(111) surface. The nature of adsorbed intermediates (COad) and the electrocatalytic properties (the onset of CO2 formation) were studied by FTIR spectroscopy. The results show that Pd has a unique catalytic activity for HCOOH oxidation, with Pd surface atoms being about four times more active than Pt surface atoms at 0.4 V. FTIR spectra reveal that on Pt atoms adsorbed CO is produced from dehydration of HCOOH, whereas no CO adsorbed on Pd can be detected although a high production rate of CO2 is observed at low potentials. This indicates that the reaction can proceed on Pd at low potentials without the typical "poison" formation. In contrast to its high activity for formic acid oxidation, the Pd film is completely inactive for methanol oxidation. The FTIR spectra show that neither adsorbed CO is formed on the Pd sites nor significant amounts of CO2 are produced during the electrooxidation of methanol. (C) 2004 Elsevier B.V. All rights reserved.