Perovskite Oxides: Materials Science in Catalysis

In a time of growing need for catalysts, perovskites have been rediscovered as a family of catalysts of such great diversity that a broad spectrum of scientific disciplines have been brought to bear in their study and application. Because of the wide range of ions and valences which this simple structure can accommodate, the perovskites lend themselves to chemical tailoring. It is relatively simple to synthesize perovskites because of the flexibility of the structure to diverse chemistry. Many of the techniques of ceramic powder preparation are applicable to perovskite catalysts. In their own right, they are therefore of interest as a model system for the correlation of solid-state parameters and catalytic mechanisms. Such correlations [See figure in the PDF file] have recently been found between the rate and selectivity of oxidation-reduction reactions and the thermodynamic and electronic parameters of the solid. For commercial processes such as those mentioned in the introduction, perovskite catalysts have not yet proven to be practical. Much of the initial interest in these catalysts related to their use in automobile exhaust control. Current interest in this field centers on noble metalsubstituted perovskites resistant to S poisoning for single-bed, dual-bed, and three-way catalyst configurations. The formulations commercially tested to date have shown considerable promise, but long-term stability has not yet been achieved. A very large fraction of the elements that make up presently used commercial catalysts can be incorporated in the structure of perovskite oxides. Conversely, it is anticipated that perovskite oxides, appropriately formulated, will show catalytic activity for a large variety of chemical conversions. Even though this expectation is by no means a prediction of commercial success in the face of competition by existing catalyst systems, it makes these oxides attractive models in the study of catalytic chemical conversion. By appropriate formulation many desirable properties can be tailored, including the valence state of transition metal ions, the binding energy and diffusion of O in the lattice, the distance between active sites, and the magnetic and conductive properties of the solid. Only a very small fraction of possible perovskite formulations have been explored as catalysts. It is expected that further investigation will greatly expand the scope of perovskite catalysis, extend the understanding of solid-state parameters in catalysis, and contribute to the development of practical catalytic processes.