Probing catalytic pathways in ultrahigh vacuum and under realistic conditions by infrared spectroscopy

COLL 304

Wilfred T. Tysoe, Department of Chemistry and Laboratory for Surface Studies, UW-Milwaukee, 3210 N Cramer St, Milwaukee, WI 53211 and D. J. Stacchiola, Department of Chemistry and Laboratory for Surface Studies, University of Wisconsin-Milwaukee, 3210 N. Cramer St., Milwaukee, WI 53211.
The ultrahigh-vacuum reaction pathways for palladium-catalyzed acetylene trimerization and hydrogenation, and ethylene hydrogenation are compared with those occurring under realistic, high-pressure conditions. These are selected since a model Pd(111) single crystal sample provides a good model for the working catalysts. In addition, all of the reactions proceed in ultrahigh vacuum allowing the reaction pathway to be studied in detail. The nature of the surface intermediates is probed using reflection-absorption infrared spectroscopy (RAIRS) where, for example, it is shown that ethylene is di-σ-bonded on clean Pd(111), but forms a more weakly bound π-bonded species on a hydrogen pre-covered surface, an effect that is shown to be due to subsurface hydrogen. The nature of the catalyst surface is monitored under reaction conditions using photoelastic modulation RAIRS, which effectively removes contributions from the gas phase, while allowing surface species to be detected.