Regular arrays of Pd and PdAu clusters on ultrathin alumina films for reactivity studies.

Hexagonal arrays of Pd and PdAu clusters are produced by condensation of metal vapors under UHV on a nanostructured alumina ultrathin film at 320 K. The alumina presents a hexagonal network of point defects that are nucleation centers for Pd. The growth of the Pd clusters is uniform leading to a very narrow size distribution in the range of size of few atoms to about 400 atoms. The number density of clusters is fixed by the density of nodes of the nanostructure of the alumina film (6.5 × 10(12) cm(-2)). The PdAu bimetallic particles grow in a two-steps process. First Pd is deposited then Au is deposited and grows exclusively on the preformed Pd clusters. The size and the composition of the clusters are independently controlled by the amounts of the deposited metals. The shape, size, density and organization of the clusters are studied in situ by STM. The long range order is studied in situ by Grazing Incidence Small Angle X-ray Scattering (GISAXS). The organization of the arrays of clusters is stable up to 600 K. These arrays of Pd and PdAu clusters on alumina are well suited model catalysts to study the effects of size, shape and composition on their reactivity.

Topography and work function measurements of thin MgO(001) films on Ag(001) by nc-AFM and KPFM.

The surface topography and local surface work function of ultrathin MgO(001) films on Ag(001) have been studied by noncontact atomic force microscopy (nc-AFM) and Kelvin probe force microscopy (KPFM). First principles calculations have been used to explain the contrast formation of nc-AFM images. In agreement with literature, thin MgO films grow in islands with a quasi rectangular shape. Contrary to alkali halide films supported on metal surfaces, where the island heights can be correctly measured, small MgO islands are either imaged as depressions or elevations depending on the electrostatic potential of the tip apex. Correct island heights therefore cannot be given without knowing the precise contrast formation discussed in this paper. KPFM shows a silver work function which is reduced by the MgO islands. The values for the work function differences for one and two layer thin films are -1.1 and -1.4 eV, respectively, in good agreement with recent calculations and experiments.

Preparation of regular arrays of bimetallic clusters with independent control of size and chemical composition.

Regular arrays of bimetallic clusters have been prepared by atomic deposition, under UHV, on a nanostructured ultrathin alumina film. The alumina films are obtained by oxidation at 1000 K of a Ni3Al (111) surface. They present two regular hexagonal superstructures with lattice parameters of 2.4 and 4.1 nm. Pd clusters nucleate exclusively on the 4.1 nm superstructure forming regular arrays of clusters extending on the whole (1 cm2) substrate. Gold deposited on a previously formed Pd clusters array, condenses exclusively on the Pd clusters in forming a regular array of bimetallic AuPd clusters with a narrow size distribution. The size and the composition of the AuPd clusters can be controlled independently. Gold clusters nucleates also on the 4.1 nm superstructure but they can escape from the nucleation sites and coalesce with other gold clusters. By condensing Pd on the preformed Au clusters, PdAu clusters are formed together with pure Pd clusters nucleated on the free sites of the 4.1 nm superstructure of the alumina film.

Environmental electron microscopy (ETEM) for catalysts with a closed E-cell with carbon windows.

In a standard high-resolution electron microscope (Jeol 3010), an environmental sample holder designed by Jeol, has been used for in situ observations at the atomic scale of catalysts, during a chemical reaction. Experiments have been performed in H(2) and O(2) at a pressure up to 4 mbar at room temperature, and in the case of H(2), at various temperatures until 350 degrees C. For the first time, Au and Pd clusters supported on TiO(2) and amorphous carbon have been observed with a windows-cell environmental electron microscopy (ETEM) system, with the resolution of the (1 1 1) lattice fringes. Au clusters have been cleaned in H(2) and have got the equilibrium shape of the fcc crystals during annealing. The same Au particles can be observed during successive treatments under O(2) and H(2). For Pd clusters in situ exposed to O(2) , the adhesion has decreased.

Fluctuations and bistabilities on catalyst nanoparticles.

We show that coverage fluctuations on catalyst particles can drastically alter their macroscopic catalytic behavior. Scrutinizing the occurrence of kinetic bistabilities, it is demonstrated by molecular beam experiments on model catalysts that macroscopically observable bistabilities vanish completely with decreasing particle size, as previously predicted by theory. The effect is attributed to fluctuation-induced transitions between two kinetic reaction regimes, with a transition rate controlled by both particle size and surface defects. These results suggest that fluctuation-induced effects represent a general phenomenon affecting the reaction kinetics on nanostructured surfaces.