Abstract
The reactions of neopentane, n-butane, propane, and n-pentane in the presence of an excess of hydrogen have been studied on evaporated Pd/Au-on-mica films. The characterization of films showed that they were predominantly (111) oriented. The selectivity in hydrogenolysis of all hydrocarbons decreased markedly with an increase in the content in Au. The catalytic activity for isomerization of neopentane and n-butane was higher for ca. 10 at.% Au alloys than for pure Pd. This finding appears to support the mechanism involving 1,2-bond shift isomerization at one metal site by McKervey et al. [ J. Catal. 30, 330 (1973)]. Additional experiments with CH 4/D 2 and neopentane/D 2 exchange over Pd-Au(111) alloys at higher temperatures showed considerable difficulties in forming carbene adspecies which could be responsible for another isomerization route. The isotopic exchange between cyclopentane and deuterium over (111) oriented Pd-Au alloys showed that the rate of multiple exchange goes through a gentle maximum for ca. 10 at.% Au. At the same time no special catalytic role of the surface sites of a low coordination number is seen. It is speculated that the rollover process may involve similar intermediate species as in alkene hydrogenation. The relative importance of ensemble size vs electronic effects in the Pd-Au alloys for various reactions is discussed.
Published Version
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