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.

Mixed ionic-electronic conducting (MIEC) ceramic-based membranes for oxygen separation

Catalytic partial oxidation of methane has been reviewed with an emphasis on the reaction mechanisms over transition metal catalysts. The thermodynamics and aspects related to heat and mass transport is also evaluated, and an extensive table on research contributions to methane partial oxidation over transition metal catalysts in the literature is provided. Presented are both theoretical and experimental evidence pointing to inherent differences in the reaction mechanism over transition metals. These differences are related to methane dissociation, binding site preferences, the stability of OH surface species, surface residence times of active species and contributions from lattice oxygen atoms and support species. Methane dissociation requires a reduced metal surface, but at elevated temperatures oxides of active species may be reduced by direct interaction with methane or from the reaction with H, H2, C or CO. The comparison of elementary reaction steps on Pt and Rh illustrates that a key factor to produce hydrogen as a primary product is a high activation energy barrier to the formation of OH. Another essential property for the formation of H2 and CO as primary products is a low surface coverage of intermediates, such that the probability of O–H, OH–H and CO–O interactions are reduced. The local concentrations of reactants and products change rapidly through the catalyst bed. This influences the reaction mechanisms, but the product composition is typically close to equilibrated at the bed exit temperature.

A review of catalytic partial oxidation of methane to synthesis gas with emphasis on reaction mechanisms over transition metal catalysts

This article provides a perspective on solid oxide fuel cells operating at low temperature, defined here to be the range from ∼400 °C to 650 °C. These low-temperature solid oxide fuel cells (LT-SOFCs) have seen considerable research and development and are widely viewed as the “next generation” technology, following the 650–850 °C SOFCs that are currently undergoing commercialization. LT-SOFCs have potential advantages for conventional SOFC applications such as stationary power generation, and may be viable for new portable and transportation power applications, along with electrolytic fuel production and energy storage. The characteristics of electrolyte and electrode materials are reviewed, with a focus on materials that have demonstrated good properties and cell performance at low temperature. Only oxygen-ion-conducting electrolytes are considered here. Anode materials are discussed, primarily the various Ni–cermet anode compositions that yield good low-temperature performance. Mixed ionically and electronically conducting cathode materials are described in detail, reflecting the extensive research activity that has aimed at providing useful oxygen reduction kinetics at low operating temperature. Cell design, materials compatibility, processing methods, and resulting microstructures are discussed, along with their role in determining cell performance. Results from state of the art LT-SOFCs are presented, and future prospects are discussed.

A perspective on low-temperature solid oxide fuel cells

Dense ceramic membranes for methane conversion

The partial oxidation of methane to synthesis gas (syngas, CO + H2) was performed in a mixed-conducting perovskite dense membrane reactor at 850°C, in which oxygen was separated from air and simultaneously fed into the methane stream. Steady-state oxygen permeation rates for La1-xA′xFe0.8 Co0.2O3-δ perovskite membranes in nonreacting air/helium experiments were in the order of A′x = Ba0.8 > Ba0.6 > Ca0.6 > Sr0.6. Deep oxidation products were obtained from a La0.2 Ba0.8 Fe0.8 Co0.2 O3–δ disk-shaped membrane reactor without catalyst, with a 4.6% CH4 inlet stream. These products were further reformed to syngas when a downstream catalytic bed was added. Packing the 5% Ni/Al2O3 catalyst directly on the membrane reaction-side surface resulted in a slow fivefold increase in O2 permeation, and a fourfold increase in CH4 conversion. XRD, EDS, and SEM analyses revealed structure and composition changes on the membrane surfaces. Oxygen continuously transported from the air side appeared to stabilize the membrane interior, and the reactor was operated for up to 850 h.

Dense perovskite membrane reactors for partial oxidation of methane to syngas

La1-xA′xFe0.8Co0.2O3-δ (A′= Ca, Sr, Ba) perovskite powders were synthesized to attain the desired properties of high O2 flux and stability under reducing conditions. Steady-state oxygen permeation rates for La1-xA′xFe0.8-Co0.2O3-δ perovskite membranes in nonreacting experiments with air on one side and helium on the other side of the membrane were in the order A′x= Ba0.8 > Ba0.6 > Ca0.6 > Sr0.6. Partial oxidation of methane to syngas (CO + H2) was performed in a dense La0.2Ba0.8Fe0.8Co0.2O3-δ membrane reactor at 850°C in which oxygen was separated from air and simultaneously fed into the methane stream. The reducing atmosphere affected the membrane reaction-side surface while barium enrichment occurred on the air-side surface. Oxygen continuously transported from the air side appeared to stabilize the membrane interior, and the reactor was operated for up to 850 h.

Dense Perovskite, La1-xA′xFe1-yCoyO3-δ (A′= Ba, Sr, Ca), Membrane Synthesis, Applications, and Characterization

A two-dimensional nonisothermal mathematical model has been developed to simulate a tube-and-shell configuration, catalytic membrane reactor. The three-layer membrane consists of an inert large-pore support, an o2 semipermeable dense perovskite layer and a porous catalytic layer. The model is applied to the simulation of the partial oxidation or methane to syngas (oxyreforming). The membrane reactor simultaneously supplies oxygen to the catalytic reaction along the reactor length, and separates oxygen from the air feed, using a dense perovskite layer which is a mixed conductor, thus allowing rapid oxygen permeation without the use of an external circuit. Two configurations of catalytic membrane reactors are simulated, for both bench-scale and industrial-scale conditions. Comparisons are made to the conventional fixed-bed reactor, and to membrane reactors which are isothermal, adiabatic or wall-cooled. The simulation results imply that the temperature rise in exothermic partial oxidation reactions...

Modeling and simulation of a nonisothermal catalytic membrane reactor

La 1-x A' x Fe 0.8 Co 0.2 O 3-δ (A'=Ca, Sr, Ba) perovskite powders were synthesized to attain the desired properties of high O 2 flux and stability under reducing conditions. Steady-state oxygen permeation rates for La 1-x A' x Fe 0.8 -Co 0.2 O 3-δ perovskite membranes in nonreacting experiments with air on one side and helium on the other side of the membrane were in the order A' x =Ba 0.8 >Ba 0.6 >Ca 0.6 >Sr 0.6 . Partial oxidation of methane to syngas (CO+H 2 ) was performed in a dense La 0.2 Ba 0.8 Fe 0.8 Co 0.2 O 3-δ membrane reactor at 850°C in which oxygen was separated from air and simultaneously fed into the methane stream. The reducing atmosphere affected the membrane reaction-side surface while barium enrichment occurred on the airside surface. Oxygen continuously transported from the air side appeared to stabilize the membrane interior, and the reactor was operated for up to 850 h.

Chung-Yi Tsai

Papers

Dense perovskite membrane reactors for partial oxidation of methane to syngas

Dense Perovskite, La1-xA′xFe1-yCoyO3-δ (A′= Ba, Sr, Ca), Membrane Synthesis, Applications, and Characterization

Modeling and simulation of a nonisothermal catalytic membrane reactor

Dense perovskite, La1-xA'xFe1-yCoyO3-δ (A' = Ba, Sr, Ca), membrane synthesis, applications, and characterization