Ultrathin metal films and particles on oxide surfaces: structural, electronic and chemisorptive properties

Surface studies of supported model catalysts

http://w0.rz-berlin.mpg.de/hjfdb/pdf/260e.pdf

Metal deposits on well-ordered oxide films

Ultrathin oxide films on metals offer new opportunities for the design of supported nanoclusters with potential use in catalysis. This requires a characterization at the atomistic level of the structure and composition of the thin film, of its morphology and defect structure. A proper selection of metal/oxide interface, film thickness, lattice mismatch, etc. makes it possible to prepare collections of supported metal particles with novel properties. This critical review describes some illustrative examples, emphasizes the role of the interplay between theory and experiment, and relates some recent findings related to the possibility to control the charge state of a supported nanoparticle on an ultrathin oxide film (211 references).

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Oxide ultra-thin films on metals: new materials for the design of supported metal catalysts

The photochemistry of small molecules on well-defined metal surfaces has been the subject of intense research for more than three decades.1 This field is of interest because it rests on the superposition of two influences. On one hand, new reaction channels can become possible by electronic excitation, which are usually not accessible by thermal activation. On the other hand, compared to molecular photochemistry in the gas phase, interactions of molecules with solid substrates open unique pathways of photoexcitation and photoreaction not accessible in homogeneous reactions. This is primarily due to the fact that the bonding interactions with the substrate modify not only the ground state but also the electronically excited states of the adsorbates. In addition, the very rapid exchange of excitation energy between adsorbates and substrate, in particular on metal and semiconductor surfaces, can lead to fast quenching of excited adsorbate states by transfer of charge and/or energy from the adsorbates to the substrate. Furthermore, excitation of adsorbates by hot (excited) electrons produced by photoabsorption in the substrate plays an important role as it induces charge and energy transfer in the opposite direction, from the substrate to adsorbates. Well-defined metal surfaces covered by adsorbate layers under ultrahigh vacuum (UHV) conditions provide systems which are well characterized in all aspects, particularly regarding geometry and electronic structure. The fact that such layers usually consist of molecules which are naturally aligned on the surface2 makes surface photochemistry a powerful alternative to the stereodynamic control of chemical reactions by optically aligned molecular beams.3 Well-defined adsorbate systems thus provide unique playgrounds for surface photochemistry.

http://w0.rz-berlin.mpg.de/hjfdb/pdf/449e.pdf

Photochemistry on Metal Nanoparticles

Small metal particles have strongly size-dependent properties, which - in the case of supported particles - are also influenced by the particle substrate interaction. We have investigated such effects for Pd deposited on a thin alumina film grown on NiAl(i10) by probing the adsorption behaviour of CO. Structure and size of the metal islands were varied by employing different substrate temperatures during evaporation. We found that at 90 K small, disordered aggregates are formed, whereas deposition at 300 K results in larger crystallites with (111) facets. The CO thermal desorption spectra show a size-dependent behaviour which can be attributed to a higher degree of CO coordination with decreasing particle size. The results are compared with the corresponding behaviour of Pt. In contrast to Pd, Pt leads to a strong interaction with the substrate at 300 K. This gives rise to a desorption feature of CO in a temperature range which is typical for transition metal oxides.

G. Graw

Papers

The growth and properties of Pd and Pt on Al2O3/NiAl(110)