Carbon supported Ru-Se as methanol tolerant catalysts for DMFC cathodes. Part I: preparation and characterization of catalysts

Carbon supported Ru (x) Se (y) O (z) catalysts were prepared from Ru-3(CO)(12) and RuCl3 center dot xH(2)O as ruthenium precursors and H2SeO3 and SeCl4 as the selenium sources. Highly active catalysts for the oxygen reduction reaction (ORR) in direct methanol fuel cells (DMFC) were obtained via a multi-step preparation procedure consisting of a CO2-activation of the carbon support prior to the preparation of a highly disperse Ru particles catalyst powder that is subsequently modified by Se. Ultimately, an excess of Se was removed during a final thermal annealing step at 800 degrees C under forming gas atmosphere. The morphology of the catalysts was analyzed by transmission electron microscopy (TEM) and X-ray diffraction (XRD), which shows that the catalysts consist of crystalline Ru-particles with sizes ranging from 2 to 4 nm exhibiting a good dispersion over the carbonaceous support. The corresponding catalytic activity in the process of oxygen reduction was analyzed by cyclic voltammetry (CV) and rotating disk electrode (RDE) measurements. The nature of the carbon support used for the preparation of RuSe cathode catalysts is of significant importance for the activity of the final materials. Catalysts supported on CO2-activated Black Pearls 2000 gave the highest ORR-activity. Se stabilizes the Ru-particles against bulk oxidation and actively contributes to the catalytic activity. An exceptional property of the carbon supported Ru-particles modified with Se is their resistance to coalescence up to temperatures of 800 degrees C under inert or reducing conditions. Additional effects of Se-modification are the enhanced stability towards electrochemical oxidation of Ru and a lowering of the H2O2 formation in the ORR