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.

Catalytic removal of NO

Biomass pyrolysis kinetics: A comparative critical review with relevant agricultural residue case studies

Catalysts for chemical and electrochemical reactions underpin many aspects of modern technology and industry, from energy storage and conversion to toxic emissions abatement to chemical and materials synthesis. This role necessitates the design of highly active, stable, yet earth-abundant heterogeneous catalysts. In this Review, we present the perovskite oxide family as a basis for developing such catalysts for (electro)chemical conversions spanning carbon, nitrogen, and oxygen chemistries. A framework for rationalizing activity trends and guiding perovskite oxide catalyst design is described, followed by illustrations of how a robust understanding of perovskite electronic structure provides fundamental insights into activity, stability, and mechanism in oxygen electrocatalysis. We conclude by outlining how these insights open experimental and computational opportunities to expand the compositional and chemical reaction space for next-generation perovskite catalysts.

http://science.sciencemag.org/content/sci/358/6364/751.full.pdf

Perovskites in catalysis and electrocatalysis

ICTAC Kinetics Committee recommendations for collecting experimental thermal analysis data for kinetic computations

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.

https://science.sciencemag.org/content/sci/195/4281/827.full.pdf

Perovskite oxides: materials science in catalysis.

Oxygen stoichiometry in Ba2YCu3Ox

The effects of sample size and heating rate on the kinetics of the thermal decomposition of CaCO3

The congruent composition of LiNbO/sub 3/ was determined precisely by correlating crystal growth compositions with the Curie temperatures of samples quenched from a melt before and after crystal growth and of various sections of crystals grown from that melt. The initial melt composition was determined by control of Li/sub 2/CO/sub 3/ and Nb/sub 2/O/sub 5/ contents. The melt compositions were varied from 47 to 49 mol% Li/sub 2/O. The variation of T /SUB c/ with melt composition was found to follow T /SUB c/ = 9095.2 - 369.05C + 4.228C/sup 2/, where C is mol% Li/sub 2/O. High-temperature DTA was used to determine T /SUB c/ with a precision of + or - 2/sup 0/C. Above 1000/sup 0/C the Li-rich phase boundary was found to be a function of temperature by determining the weight gain after complete lithiation of congruently grown crystals. This boundary curves slightly toward lower Li/sub 2/O content as temperature increases. The congruent composition of LiNbO/sub 3/ contains 48.45 mol% Li/sub 2/O and has a measured Curie temperature of 1138/sup 0/ + or - 2/sup 0/C.

Congruent Composition and Li-Rich Phase Boundary of LiNbO3

Dilatometry, high-temperature x-ray diffraction, differential thermal analysis, and differential scanning calorirmetry have been performed on LaGaO3, NdGaO3, PrGaO3, SmAlO3, and LaAlO3 single crystals grown by the Czochralski technique. First order phase transitions have been located at 145°C for LaGaO3 and 785°C for SmAlO3, and ΔH has been measured for the LaGaO3 transition. Second order transitions have been identified for LaGaO3, PrGaO3, NdGaO3, and LaAlO3. The usefulness of these compounds as substrates for high temperature superconducting films is discussed in terms of thermal expansion matching.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/S0884291400008566

P.K. Gallagher

Papers

Perovskite oxides: materials science in catalysis.

Oxygen stoichiometry in Ba2YCu3Ox

The effects of sample size and heating rate on the kinetics of the thermal decomposition of CaCO3

Congruent Composition and Li-Rich Phase Boundary of LiNbO3

Thermal analysis of rare earth gallates and aluminates