Oxidation Catalysts Based on Antimony Mixed Oxides with Rutile-Type Structures

Abstract

Several authors have correlated catalyst structure to catalytic behavior in selective oxidation reactions. Sleight [1] reviewed the importance of the scheelite structure for the allylic oxidation and ammonoxidation of olefins; Grasselli and co-workers [2–4] extensively examined the relationship between structure and catalytic activity of bismuth-molybdates, uranium-antirnonates, and bismuth-cerium molybdates. Bordes and Courtine [5] correlated the activity in mild oxidation of 1-butene to the properties of the structure of vanadium-phosphorus oxides. However, little attention has been given in the literature to the role of the rutile structure in allylic oxidation reactions even though the high activity and selectivity of antimony oxides stabilized in matrices with rutile structure (SnO₂ and FeSbO₄) in olefins oxidation and ammonoxidation have been known for several years. Furthermore, Tables 1 and 2 indicate that the kinetic and catalytic behavior of antimony-based catalysts in allylic oxidation reactions are very different from that of molybdate-based catalysts. This suggests that antimony- and molybdate-based catalysts are two distinct classes of catalysts of allylic oxidation, in agreement with a recent suggestion by Grasselli et al. [13].