CO oxidation activity of Pt/CeO2 catalysts below 0ºC: Platinum loading effects

Reducing the operating temperature of oxidation catalysts is important for designing energy efficient processes, extending catalyst lifetime, and abating pollutants, especially in cold climates. Herein, high CO oxidation activity at sub-ambient temperatures is reported for Pt/CeO2 catalysts with high content of Pt in the form of dispersed Pt2+ and Pt4+ centers. Whereas the reference 1 wt%Pt catalyst was active for CO oxidation only above 100ᵒC, the 8 and 20 wt%Pt catalysts converted 60 and 90 % of CO, respectively, below 0ᵒC. Ionic platinum was shown to facilitate oxygen release from ceria and lower the light-off temperature of the reaction occurring through the Mars-van-Krevelen mechanism. However, the remarkable activity observed at sub-ambient temperatures for the ≥8 wt%Pt catalysts is proposed to involve O2 and CO reactants weakly adsorbed on PtOx clusters. The synergies between ionic platinum and nanostructured ceria reported in this work advance the knowledge-driven design of catalysts for low-temperature oxidation reactions

Sub-surface Oxygen and Surface Oxide Formation at Ag(111): A Density-functional Theory Investigation

To help provide insight into the remarkable catalytic behavior of the oxygen/silver system for heterogeneous oxidation reactions, purely sub-surface oxygen, and structures involving both on-surface and sub-surface oxygen, as well as oxide-like structures at the Ag(111) surface have been studied for a wide range of coverages and adsorption sites using density-functional theory. Adsorption on the surface in fcc sites is energetically favorable for low coverages, while for higher coverage a thin surface-oxide structure is energetically favorable. This structure has been proposed to correspond to the experimentally observed (4x4) phase. With increasing O concentrations, thicker oxide-like structures resembling compressed Ag2O(111) surfaces are energetically favored. Due to the relatively low thermal stability of these structures, and the very low sticking probability of O2 at Ag(111), their formation and observation may require the use of atomic oxygen (or ozone, O3) and low temperatures. We also investigate diffusion of O into the sub-surface region at low coverage (0.11 ML), and the effect of surface Ag vacancies in the adsorption of atomic oxygen and ozone-like species. The present studies, together with our earlier investigations of on-surface and surface-substitutional adsorption, provide a comprehensive picture of the behavior and chemical nature of the interaction of oxygen and Ag(111), as well as of the initial stages of oxide formation.Comment: 17 pages including 14 figures, Related publications can be found at http://www.fhi-berlin.mpg.de/th/paper.htm