Controlling the adsorption kinetics via nanostructuring: Pd nanoparticles on TiO2 nanotubes.

Activity and selectivity of supported catalysts critically depend on transport and adsorption properties. Combining self-organized porous oxide films with different metal deposition techniques, we have prepared novel Pd/TiO(2) catalysts with a new level of structural control. It is shown that these systems make it possible to tune adsorption kinetics via their nanostructure. Self-organized TiO(2) nanotubular arrays (TiNTs) prepared by electrochemical methods are used as a support, on which Pd particles are deposited. Whereas physical vapor deposition (PVD) in ultrahigh vacuum (UHV) allows us to selectively grow Pd particles at the tube orifice, Pd/TiNT systems with homogeneously distributed Pd aggregates inside the tubes are available by particle precipitation (PP) from solution. Both methods also provide control over particle size and loading. Using in-situ infrared reflection absorption spectroscopy (IRAS) and molecular beam (MB) methods, we illustrate the relation between the nanostructure of the Pd/TiNT systems and their adsorption kinetics. Control over the metal nanoparticle distribution in the nanotubes leads to drastic differences in adsorption probability and saturation behavior. These differences are rationalized based on differences in surface and gas phase transport resulting from their nanostructure. The results suggest that using carefully designed metal/TiNT systems it may be possible to tailor transport processes in catalytically active materials.