Platinum is the most versatile element in catalysis, but it is rare and its high price limits large-scale applications, for example in fuel-cell technology. Still, conventional catalysts use only a small fraction of the Pt content, that is, those atoms located at the catalyst's surface. To maximize the noble-metal efficiency, the precious metal should be atomically dispersed and exclusively located within the outermost surface layer of the material. Such atomically dispersed Pt surface species can indeed be prepared with exceptionally high stability. Using DFT calculations we identify a specific structural element, a ceria "nanopocket", which binds Pt(2+) so strongly that it withstands sintering and bulk diffusion. On model catalysts we experimentally confirm the theoretically predicted stability, and on real Pt-CeO2 nanocomposites showing high Pt efficiency in fuel-cell catalysis we also identify these anchoring sites.
The concept of single atom catalysis offers maximum noble metal efficiency for the development of lowcost catalytic materials. Among possible applications are catalytic materials for proton exchange membrane fuel cells. In the present review, recent efforts towards the fabrication of single atom catalysts on nanostructured ceria and their reactivity are discussed in the prospect of their employment as anode catalysts.The remarkable performance and the durability of the ceria-based anode catalysts with ultra-low Pt loading result from the interplay between two states associated with supported atomically dispersed Pt and subnanometer Pt particles. The occurrence of these two states is a consequence of strong interactions between Pt and nanostructured ceria that yield atomically dispersed species under oxidizing conditions and sub-nanometer Pt particles under reducing conditions. The square-planar arrangement of four O atoms on {100} nanoterraces has been identified as the key structural element on the surface of the nanostructured ceria where Pt is anchored in the form of Pt 2+ species. The conversion of Pt 2+ species to subnanometer Pt particles is triggered by a redox process involving Ce 3+ centers. The latter emerge due to either oxygen vacancies or adsorption of reducing agents. The unique properties of the sub-nanometer Pt particles arise from metal-support interactions involving charge transfer, structural flexibility, and spillover phenomena. The abundance of specific adsorption sites similar to those on {100} nanoterraces determines the ideal (maximum) Pt loading in Pt-CeO x films that still allows reversible switching between the atomically dispersed Pt and sub-nanometer particles yielding high activity and durability during fuel cell operation.
Epitaxial GaN layers grown on sapphire contain a very large density of defects
(threading dislocations, stacking faults, inversion domain boundaries, . . .). Among
these defects, we have performed the analysis of the basal stacking faults by
high resolution transmission electron microscopy. Two faults, I1 and I2,
were identified. The formation of the I1 fault is based on the
climb-dissociation process of the (1/3)⟨11-20⟩ or of the
[0001] perfect dislocations whereas the I2 fault is due to the shear of the
structure leading to a partial dislocation loop.
The interaction of Pt with CeO(2) layers was investigated by using photoelectron spectroscopy. The 30 nm thick Pt doped CeO(2) layers were deposited simultaneously by rf-magnetron sputtering on a Si(001) substrate, multiwall carbon nanotubes (CNTs) supported by a carbon diffusion layer of a polymer membrane fuel cell and on CNTs grown on the silicon wafer by the CVD technique. The synchrotron radiation X-ray photoelectron spectra showed the formation of cerium oxide with completely ionized Pt(2+,4+) species, and with the Pt(2+)/Pt(4+) ratio strongly dependent on the substrate. The TEM and XRD study showed the Pt(2+)/Pt(4+) ratio is dependent on the film structure.
An overview is given about microstructure and composition analyses of InGaN quantum wells embedded in Ga(Al)N barriers to study the mechanisms which determine the In distribution in epitaxially grown InGaN layers. The applied technique is transmission electron microscopy (TEM). The main prerequisite for this work was the development of a technique based on high-resolution lattice fringe images that allows quantitative chemical analyses of InGaN on an atomic scale. A large variety of samples was investigated that were produced by molecular beam epitaxy (MBE) and metal-organic vapor phase epitaxy (MOVPE). The effect of the deposition temperature, growth rate, strain and high-temperature annealing treatments on the average In concentration and In distribution was studied to assess the influence of phase separation, In surface segregation and In desorption. Composition fluctuations in InGaN are always observed on two different lateral scales independent of the growth technique and particular set of growth parameters but the strength of the composition fluctuations can be influenced by the details of the growth.
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