On the CO tolerance of novel colloidal PdAu/carbon electrocatalysts

The synthesis and characterization (physical and electrochemical) of novel PdAu/Vulcan XC72 electrocatalysts are described. The catalysts were prepared via deposition and activation of preformed bimetallic colloidal precursors. Physical characterization of the catalysts involved high-resolution transmission electron microscopy and powder X-ray diffraction. Electrochemically, the PdAu-catalysts were characterized by means of the thin-film rotating disk method and by differential electrochemical mass spectrometry. H₂, CO and CO/H₂ oxidations on PdAu/Vulcan electrodes with different bulk compositions were used as probe reactions to determine the CO tolerance of this catalyst system and its physical origin. We propose that the CO-tolerance mechanism at low overpotentials for PdAu/Vulcan electrodes is governed by both a lower CO steady-state surface coverage compared to PtRu/Vulcan due to a lower CO adsorption energy and finite CO oxidation rates, which both result in free surface sites for H₂ oxidation to take place. At elevated temperatures (60°C) this effect is more pronounced, providing more free active Pd sites for H₂ oxidation. CO/H₂ oxidation measurements (1000 and 250ppm CO) showed the superior activity of PdAu compared with a state-of-the-art PtRu catalyst at technically relevant potentials, especially in Pd-rich alloys.