Metamorphosis of palladium and its relation to selectivity in the Rosenmund reaction

Abstract

Drastic changes in morphology and particle sizes of the Pd particles were detected during the classical catalyst pretreatment. These changes are connected to the increase in selectivity as well as to the problems encountered in the Rosenmund reaction. A major action of the poison in Rosenmund reactions was found to be the acceleration of the initial reconstruction of the surface of fresh catalysts to prevent overreduction. The instability of the Pd under reaction conditions appears to be responsible for typical problems encountered with the Rosenmund reaction such as irreproducibility and catalyst deactivation during the reaction. With the use of Pd single crystals stepped and kinked surfaces were found to be active for hydrogenolysis of acid chlorides to aldehydes. Transmission electron microscopy and diffraction have been employed to characterize the change in dispersion and structure of Pd particles on carbon supports after various pretreatments.