Over the past several years, cerium oxide and CeO2-containing materials have come under intense scrutiny as catalysts and as structural and electronic promoters of heterogeneous catalytic reactions. Recent developments regarding the characterization of ceria and CeO2-containing catalysts are critically reviewed with a special focus towards catalyst interaction with small molecules such as hydrogen, carbon monoxide, oxygen, and nitric oxide. Relevant catalytic and technological applications such as the use of ceria in automotive exhaust emission control and in the formulation of SO x reduction catalysts is described. A survey of the use of CeO2-containing materials as oxidation and reduction catalysts is also presented.

Catalytic Properties of Ceria and CeO2-Containing Materials

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.

The open literature concerning chemical and mechanistic aspects of the selective catalytic reduction of NO by ammonia (SCR process) on metal oxide catalysts is reviewed. Catalytic systems based on supported V2O5 (including the industrial TiO2-supported V2O5–WO3 and/or V2O5–MoO3 catalysts) and catalysts containing Fe2O3, CuO, MnOx and CrOx are considered. The results of spectroscopic studies of the adsorbed surface species, adsorption–desorption measurements, flow reactor and kinetic experiments are analyzed. The proposed reaction mechanisms are described and critically discussed. Points of convergence and of disagreement are underlined.

Chemical and mechanistic aspects of the selective catalytic reduction of NOx by ammonia over oxide catalysts: A review

Hydrogen peroxide (H2O2) is widely used in almost all industrial areas, particularly in the chemical industry and environmental protection. The only degradation product of its use is water, and thus it has played a large role in environmentally friendly methods in the chemical industry. Hydrogen peroxide is produced on an industrial scale by the anthraquinone oxidation (AO) process. However, this process can hardly be considered a green method. It involves the sequential hydrogenation and oxidation of an alkylanthraquinone precursor dissolved in a mixture of organic solvents followed by liquid–liquid extraction to recover H2O2. The AO process is a multistep method that requires significant energy input and generates waste, which has a negative effect on its sustainability and production costs. The transport, storage, and handling of bulk H2O2 involve hazards and escalating expenses. Thus, novel, cleaner methods for the production of H2O2 are being explored. The direct synthesis of H2O2 from O2 and H2 using a variety of catalysts, and the factors influencing the formation and decomposition of H2O2 are examined in detail in this Review.

http://www.sciencemadness.org/talk/files.php?pid=171164&aid=9838

Hydrogen Peroxide Synthesis: An Outlook beyond the Anthraquinone Process

The increase in atmospheric carbon dioxide is linked to climate changes; hence there is an urgent need to reduce the accumulation of CO2 in the atmosphere. The utilization of CO2 as a raw material in the synthesis of chemicals and liquid energy carriers offers a way to mitigate the increasing CO2 buildup. This review covers six important CO2 transformations namely: chemical transformations, photochemical reductions, chemical and electrochemical reductions, biological conversions, reforming and inorganic transformations. Furthermore, the vast research area of carbon capture and storage is reviewed briefly. This review is intended as an introduction to CO2, its synthetic reactions and their possible role in future CO2 mitigation schemes that has to match the scale of man-made CO2 in the atmosphere, which rapidly approaches 1 teraton.

The teraton challenge. A review of fixation and transformation of carbon dioxide

CATALYTIC CONVERSION OF METHANE TO MORE USEFUL CHEMICALS AND FUELS: A CHALLENGE FOR THE 21st CENTURY

Partial oxidation of methane to carbon monoxide and hydrogen over a Ni/Al2O3 catalyst

One of the great challenges in the field of heterogeneous catalysis is the conversion of methane to more useful chemicals and fuels. A chemical of particular importance is ethene, which can be obtained by the oxidative coupling of methane. In this reaction CH4 is first oxidatively converted into C2H6, and then into C2H4. The fundamental aspects of the problem involve both a heterogeneous component, which includes the activation of CH4 on a metal oxide surface, and a homogeneous gas-phase component, which includes free-radical chemistry. Ethane is produced mainly by the coupling of the surface-generated CH radicals in the gas phase. The yield of C2H4 and C2H6 is limited by secondary reactions of CH radicals with the surface and by the further oxidation of C2H4, both on the catalyst surface and in the gas phase. Currently, the best catalysts provide 20% CH4 conversion with 80% combined C2H4 and C2H6 selectivity in a single pass through the reactor. Less is known about the nature of the active centers than about the reaction mechanism; however, reactive oxygen ions are apparently required for the activation of CH4 on certain catalysts. There is spectroscopic evidence for surface O− or O ions. In addition to the oxidative coupling of CH4, cross-coupling reactions, such as between methane and toluene to produce styrene, have been investigated. Many of the same catalysts are effective, and the cross-coupling reaction also appears to involve surface-generated radicals. Although a technological process has not been developed, extensive research has resulted in a reasonable understanding of the elementary reactions that occur during the oxidative coupling of methane.

The Catalytic Oxidative Coupling of Methane

When methane was passed over MgO at temperatures of approximately 500/sup 0/C, methyl radicals were produced on the surface, released into the gas phase, and trapped downstream in a solid argon matrix where they were analyzed by EPR spectroscopy. Significant differences in initial activity were observed, depending on whether the MgO was pretreated under vacuum or a flow of oxygen. Vacuum conditioning led to essentially no activity while oxygen conditioning resulted in substantial radical production. The oxidant of choice was also critical. Nitrous oxide resulted in a continuous decline of activity while in the presence of oxygen the formation of radicals was at a steady state. Doping of MgO with lithium, sodium, or iron was also examined. Lithium was found to greatly increase the activity up to a doping level of approximately 15.0 wt%. Two pathways are believed to be responsible for the radical formation. Over pure MgO, intrinsic cattion vacancies react with molecular oxygen to given an O/sup -/ center which can abstract a hydrogen atom from methane to produce the methyl radical. For the lithium-doped samples, substitutional Li/sup +/ ions react with molecular oxygen to form a (Li/sup +/O/sup -/) center which is also capable of abstracting amore » hydrogen atom from methane. 28 references, 5 figures, 3 tables.« less

Formation of gas-phase methyl radicals over magnesium oxide

The partial oxidation of methane into more useful chemicals such as methanol, ethylene and benzene has been investigated extensively, although yields for these products have been poor1–4. Moreover, in several of these processes the required oxidant is N2O rather than O2. Recent work5 in our laboratory has demonstrated that lithium-doped magnesium oxide (Li/MgO) in the presence of O2 has high activity for abstracting H from CH4 to form ·CH3 radicals. This suggests that C2H6 and C2H4 (C2 compounds) are produced by a coupling between two gaseous ·CH3 radicals formed on this catalyst. We report here our success in converting CH4 to C2 compounds in high yields in conventional catalytic conditions.

Jack H. Lunsford

Papers

CATALYTIC CONVERSION OF METHANE TO MORE USEFUL CHEMICALS AND FUELS: A CHALLENGE FOR THE 21st CENTURY

Partial oxidation of methane to carbon monoxide and hydrogen over a Ni/Al2O3 catalyst

The Catalytic Oxidative Coupling of Methane

Formation of gas-phase methyl radicals over magnesium oxide

Synthesis of ethylene and ethane by partial oxidation of methane over lithium-doped magnesium oxide