Abstract.We report on a home-built detector for catalytic reaction measurements offering good gas isolation from the surrounding ultrahigh vacuum components, high sensitivity for reaction products and a fast response time of 10 ms enabling dynamic studies correlated to reactant gas pulses. The device is mounted in ultrahigh vacuum and combined with a low-temperature scanning tunneling microscope and a source for the deposition of mass-selected clusters. This combination allows for a direct correlation between surface morphology and catalytic properties of model catalysts. The performances of the new detector are illustrated by measurements on two model systems. Thermal desorption spectroscopy of CO carried out on morphologically well characterized Pt on TiO2(110)-(1×1) reveals several desorption features, which can be attributed to different surface sites. Catalytic CO oxidation performed by alternatingly pulsing isotopic CO and O2 on a Pt film on yttria stabilized zirconia reveals the CO or O rich temperature regimes. The CO2 production rate correlated with either one of the reactants can perfectly be reproduced by a kinetic reaction model giving access to the respective adsorption energies.

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Abstract. The growth of Palladium nano-clusters prepared by atomic beam deposition on prestructured highly oriented pyrolytic graphite (HOPG) surfaces has been investigated by means of scanning tunnelling microscopy (STM). Preformed nanosized pits created on the HOPG surfaces are used as localized pinning sites for Pd cluster nucleation and growth at room temperature. We succeeded in obtaining Pd clusters of nanometric size and with rather sharp size distributions. A systematic morphological study conducted by STM reveals a linear dependence between the height and the diameter of the Pd nanostructures. Finally, Pd nano-clusters stabilized on prestructured HOPG surfaces were found to be active catalysts in the Heck cross-coupling reaction.

Electrochemical promotion (EP) of CO oxidation is shown for the first time on induced bipolar Pt particles supported on yttria-stabilized zirconia (YSZ). These Pt particles are formed by sputter deposition of highpurity Pt metal followed by sintering. Conditions were chosen to stay below the percolation threshold of Pt particles. In-plane polarization of Pt particles results in a bipolar system and leads to the formation of a large number of galvanic cells partially or completely polarized. We have defined an equivalent number of active cells (n cell ) which has been estimated from the oxygen evolution reaction as a function of the applied current on the two feed electrodes. The CO oxidation rate is measured under high vacuum conditions as a function of applied current. The use of isotopically labeled oxygen allows the discrimination of the faradaic process ( 16 O from YSZ) from the non-faradaic process ( 18 O from 18 O 2 ) and to determine the faradaic efficiency (Λ) and the rate enhancement (ρ) parameters in this bipolar system. These results mark an important step in the realization of electrochemical promotion on highly dispersed catalysts.

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Abstract. Gold nanoparticles with a diameter comprised between 4 and 6 nm are stabilized in nanosized pits of well defined depth in highly oriented pyrolytic graphite (HOPG). These pits are produced by creation of artificial defects, followed by etching under a controlled oxygen atmosphere. At low Au coverage, clusters are found on the edges of the hexagonal pits maximizing the contact to dangling bonds on graphite multisteps. Larger coverage results in Au beads of surprisingly well defined shape and with a constant bead density per unit length. Most remarkable is the stability of these nanostructures under ambient conditions. Temperatures as high as 650 K do not alter the morphology of the gold clusters. Higher temperatures do not lead to a change of the cluster morphology but to catalytically driven etching of the HOPG substrate.

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