Zeolites and Related Materials as Catalyst Supports for Hydrocarbon Oxidation Reactions

Catalytic oxidation is a key technology for the conversion of petroleum-based feedstocks into useful chemicals (e.g., adipic acid, caprolactam, glycols, acrylates, and vinyl acetate) since this chemical transformation is always involved in synthesis processes. Millions of tons of these compounds are annually produced worldwide and find applications in all areas of chemical industries, ranging from pharmaceutical to large-scale commodities. The traditional industrial methods to produce large amounts of those compounds involve over-stoichiometric quantities of toxic inorganic reactants and homogeneous catalysts that operate at high temperature, originating large amounts of effluents, often leading to expensive downstream processes, along with nonrecovery of valuable catalysts that are loss within the reactant effluent. Due to the increasingly stringent environmental legislation nowadays, there is considerable pressure to replace these antiquate technologies, focusing on heterogeneous catalysts that can operate under mild reactions conditions, easily recovered, and reused. Parallelly, recent advances in the synthesis and characterization of metal complexes and metal clusters on support surfaces have brought new insights to catalysis and highlight ways to systematic catalysts design. This review aims to provide a comprehensive bibliographic examination over the last 10 years on the development of heterogeneous catalysts, i.e., organometallic complexes or metal clusters immobilized in distinct inorganic supports such as zeolites, hierarchical zeolites, silicas, and clays. The methodologies used to prepare and/or modify the supports are critically reviewed, as well as the methods used for the immobilization of the active species. The applications of the heterogenized catalysts are presented, and some case-studies are discussed in detail.