II. Structure of Perovskites 1982 A. Crystal Structure 1982 B. Nonstoichiometry in Perovskites 1983 1. Oxygen Nonstoichiometry 1983 2. Cation Nonstoichiometry 1984 C. Physical Properties 1985 D. Adsorption Properties 1986 1. CO and NO Adsorption 1986 2. Oxygen Adsorption 1987 E. Specific Surface and Porosity 1987 F. Thermal Stability in a Reducing Atmosphere 1989 III. Acid−Base and Redox Properties 1990 A. Acidity and Basicity 1990 B. Redox Processes 1991 1. Kinetics and Mechanisms 1992 2. Reduction−Oxidation Cycles 1993 C. Ion Mobility 1993 1. Oxygen Transport 1993 2. Cation Transport 1994 IV. Heterogeneous Catalysis 1995 A. Oxidation Reactions 1995 1. CO Oxidation 1995 2. Oxidation of Hydrocarbons 1996 B. Pollution Abatement 2001 1. NOx Decomposition 2001 2. Exhaust Treatment 2002 3. Stability 2004 C. Hydrogenation and Hydrogenolysis Reactions 2004 1. Hydrogenation of Carbon Oxides 2004 2. Hydrogenation and Hydrogenolysis Reactions 2006

Chemical structures and performance of perovskite oxides.

Perovskites as substitutes of noble metals for heterogeneous catalysis: dream or reality.

Publisher Summary This chapter discusses the structure and reactivity of perovskite-type oxides. Perovskite-type oxides have the general formula ABO 3 (A, cation of larger size) and are structurally similar to CaTiO 3 , the mineral that gave its name to that group of compounds. These materials are first studied because of their important physical properties such as ferro-, piezo-, and pyroelectricity, magnetism and electrooptic effects. The most numerous and most interesting compounds with the perovskite structure are oxides. Some hydrides, carbides, halides, and nitrides also crystallize with this structure. The chapter reviews only the study of oxides and their behavior in the gas solid interface and in heterogeneous catalysis. An important characteristic of perovskites, mentioned in the chapter, is their susceptibility of partial substitution in both A and B positions. This provides a wealth of isomorphic compounds that can easily be synthesized. Given the extensive range of possibilities in the tailoring of their chemical and physical properties, there is no doubt that new reactions can be studied, where these oxides can participate as catalytic agents.

Structure and Reactivity of Perovskite-Type Oxides

There is a need to reduce the use of noble metal elements—especially in the field of catalysis, where noble metals are ubiquitously applied. To this end, perovskite oxides, an important class of mixed oxide, have been attracting increasing attention for decades as potential replacements. Benefiting from the extraordinary tunability of their compositions and structures, perovskite oxides can be rationally tailored and equipped with targeted physical and chemical properties—for example, redox behavior, oxygen mobility, and ionic conductivity—for enhanced catalysis. Recently, the development of highly efficient perovskite oxide catalysts has been extensively studied. This perspective article summarizes the recent development of lanthanum-based perovskite oxides as advanced catalysts for both energy conversion applications and traditional heterogeneous reactions.

Recent Advances of Lanthanum-Based Perovskite Oxides for Catalysis

Perovskite-type materials LaCoO3 and LaCoFeO3 were prepared from their component oxides using mechano-synthesis, by a new method of preparation designated as reactive grinding. When grinding additives are used, the perovskites generated via this process are of unprecedently high specific surface area (>100 m2/g) and their surface chemical properties are of particular interest. The perovskite surface shows a large concentration of surface OHs (due to the low grinding temperature) which upon calcination leads to reformation of the materials lattice. The presence of oxygen during calcination initiates a competitive process, which stabilizes sites with an excess of electronic charge, yielding reduced Co sites upon oxygen desorption (Co2+). XPS analysis illustrates an increase in these reduced Co2+ ion concentration with calcination temperature. At high calcination temperature (>673 K), TPD studies show the release of β-oxygen originating from the bulk.

Michel Crespin

Papers

The surface chemistry of some perovskite oxides