Potential dependence of segregation and surface alloy formation of a Ru modified carbon supported Pt catalyst

Ruthenium modified carbon supported platinum catalysts have been shown to have a similar activity towards carbon monoxide oxidation as conventionally prepared bimetallic PtRu alloy catalysts. In this study the effect of the applied electrode potential and potential cycles on the location and oxidation state of the Ru species in such Ru modified Pt/C catalysts was investigated using in situ EXAFS collected at both the Ru K and Pt L₃ absorption edges. The as prepared catalyst was found to consist of a Pt core with a Ru oxy/hydroxide shell. The potential dependent data indicated alloying to form a PtRu phase at 0.05 V versus RHE and subsequent dealloying to return to the Ru oxy/hydroxide decorated Pt surface at potentials greater than 0.7 V. The Ru-O distances obtained indicate that both Ru³⁺ and Ru⁴⁺ species are present on the surface of the Pt particles at oxidising potentials; the former is characteristic of the as prepared Ru modified Pt/C catalyst and following extensive periods at potentials above 0.7 V and the latter of the Ru oxide species on the PtRu alloy.     

Characteristics of adsorbed CO and CH3OH oxidation reactions for complex Pt/Ru catalyst systems

Pt/Ru powder catalysts of the same nominal Pt to Ru composition were prepared using a range of methods resulting in different catalyst properties. Two PtRu alloy catalysts were prepared, one of which has essentially the same surface and bulk Pt to Ru composition, while the second catalyst is surface enriched with Ru. Two powders consisting of non-alloyed Pt phases and surfaces enriched with Ru were also prepared. The oxidation state of the surface Ru of the latter two catalysts is mainly metallic Ru or Ru-oxides. The catalyst consisting of Ru-oxides was formed at 500 °C. Part of this catalyst was then reduced in a H₂ atmosphere under “mild” conditions, thus catalyst properties such as particle size are not changed, as they are locked in during previous high temperature treatment. The oxidation kinetics of adsorbed CO (CO_ads) and solution CH₃OH were studied and compared to the Ru ad-metal state and Pt to Ru site distribution of the as-prepared catalysts. The kinetics of the CO_ads oxidation reaction were observed to be slower for the catalyst containing Ru-oxides as opposed to mainly Ru metal. The CH₃OH oxidation activities measured per Pt surface area, i.e., the catalytic activities are better (by ca. seven times) for the alloy catalysts than the non-alloyed Pt/Ru catalysts. The latter two catalysts showed essentially the same catalytic CH₃OH oxidation activities, i.e., independent of the Ru ad-metal oxidation state of the as-prepared catalysts. Furthermore, it is shown that CO_ads oxidation experiments can be used to extract characteristics that allow the comparison of catalytic activities for the CO_ads oxidation reaction and Pt to Ru site distribution for complex catalyst systems.     

In situ Ru K-edge EXAFS of CO adsorption on a Ru modified Pt/C fuel cell catalyst

The Ru-CO bond of CO adsorbed on a Ru modified Pt/C fuel cell catalyst has been directly probed by in situ EXAFS at the Ru K-edge, providing evidence of a CO:metal surface atom ratio greater than 1:1 and that CO is adsorbed at bridging sites associated with Ru atoms at the surface of the catalyst nanoparticles. This result illustrates the limitations of single crystal models as representations of the bonding of adsorbed species at nanoparticle surfaces.     

Production of NiO,NiO/Ag,NiO/Au,and NiO/Pt hollow spheres by using block copolymer stabilized microspheres as a template

Hollow spheres of nickel oxide (NiO) and silver, gold, and platinum nanoparticle loaded NiO composites were successfully produced by using polystyrene (PS) latexes as hard template. Due to the presence of tertiary amine based diblock copolymer stabilizer on the surface of PS, the tertiary amine functional groups provided homogene deposition of nickel hydroxide, and then the precursor NiO salt production on the surface of PS latexes with a controlled precipitation technique. Then, NiO and NiO/metal NP hollow spheres were produced by calcination at 600 °C. Thermogravimetric analysis indicated that the amounts of NiO and NiO-composite after calcination were in the range of 21.1–29.7 wt%. The diameters of metal oxide spheres were in the range of 2.0–2.7 μm and the shell thickness were in the range of 250–350 nm. These structures had very low densities due to their porous and hollow structures and had outer layers with highly rough surfaces due to formation of nanosheets, which may offer important advantages for catalysis studies.