A test reaction to assess the presence of Brönsted and the softness/hardness of Lewis acid sites in palladium supported catalysts

Abstract

Cyclic ethylene acetal of α-bromopropiophenone gives rise to three distinctive products, each one being specific to Brönsted, hard Lewis and soft Lewis sites, respectively. In the presence of Brönsted sites, hydrolysis of cyclic acetal forms the corresponding α-bromophenone. Hard or soft Lewis sites promote selectively a rearrangement of the phenyl or ethylenedioxy group to form 2-phenylpropionate ester or dioxine, respectively. This test reaction has been used to assess the influence of the support on the catalytic activity of palladium in zeolites. Three series of supports including alkali-exchanged faujasite, Beta zeolites and sepiolites have been tested. It has been observed that the nature of the zeolite plays an important role on the palladium selectivity, basic supports increasing the softness of the palladium Lewis sites. The catalytic test correlates well with electrochemical data about the reduction potential of supported palladium, XPS characterization of the oxidation state of palladium supported on the surface and activity in the Suzuki reaction.