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Abstract

This work describes hydrogen chemisorption on clean and lead modified palladium particles obtained from decomposition of PdO. TPD is used as a chemical probe to test the surface properties of several states of metallic palladium relevant in practical selective hydrogenation catalysts. These states differ in oxygen content and the presence of a lead modifier. XPS and UPS data serve as a basis for identifying the surface properties. TPD spectra show a very broad low temperature peak-likely bulk hydride decomposition-and a sharp TPD peak between 330 and 380 K. This latter can be devided into three rather poorly separated subpeaks; addition of Pb does not shift peak maxima but decreases the central subpeak and eliminates the high temperature peak completely. This points to the interaction of Pb with specific surface sites rather than to bulk alloy formation.

The enhancement of selectivity in hydrogenation obtained from lead modification is considered as a geometric site blocking effect rather than to arise from a bulk modification of the valence electronic structure of palladium metal.