Activities and stabilities of heterogeneous catalysts in selective liquid phase oxidations: recent developments Original Research Article

Different strategies for the heterogenization of redox-active elements in solid matrices are reviewed. These include framework-substituted molecular sieves, amorphous mixed oxides by grafting or sol–gel methods, grafting or tethering to the inner walls of mesoporous molecular sieves, encapsulation by ship-in-a-bottle or other techniques and ion exchange in layered double hydroxides. The different approaches are illustrated by reference to recent developments involving a variety of metal catalysts — titanium, chromium, cobalt, manganese, iron, ruthenium, tungsten, molybdenum, vanadium and tantalum — in oxidations with O2, H2O2 and RO2H as primary oxidants. Emphasis is placed on an evaluation of the stability of the various catalysts under reaction conditions, a conditio sine qua non for practical utility. Protocols for establishing heterogeneity are discussed. An analysis of experimental results leads to the conclusion that many of the systems described in the literature, particularly those involving oxometal species, are unstable towards leaching or the appropriate rigorous tests for heterogeneity have not been performed.