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

A surface science perspective on TiO2 photocatalysis

Cerium dioxide (CeO2, ceria) is becoming an ubiquitous constituent in catalytic systems for a variety of applications. 2016 sees the 40th anniversary since ceria was first employed by Ford Motor Company as an oxygen storage component in car converters, to become in the years since its inception an irreplaceable component in three-way catalysts (TWCs). Apart from this well-established use, ceria is looming as a catalyst component for a wide range of catalytic applications. For some of these, such as fuel cells, CeO2-based materials have almost reached the market stage, while for some other catalytic reactions, such as reforming processes, photocatalysis, water-gas shift reaction, thermochemical water splitting, and organic reactions, ceria is emerging as a unique material, holding great promise for future market breakthroughs. While much knowledge about the fundamental characteristics of CeO2-based materials has already been acquired, new characterization techniques and powerful theoretical methods are dee...

Fundamentals and Catalytic Applications of CeO2-Based Materials

The chemistry of copper is extremely rich because it can easily access Cu0, CuI, CuII, and CuIII oxidation states allowing it to act through one-electron or two-electron processes. As a result, both radical pathways and powerful two-electron bond forming pathways via organmetallic intermediates, similar to those of palladium, can occur. In addition, the different oxidation states of copper associate well with a large number of different functional groups via Lewis acid interactions or π-coordination. In total, these feature confer a remarkably broad range of activities allowing copper to catalyze the oxidation and oxidative union of many substrates.

Oxygen is a highly atom economical, environmentally benign, and abundant oxidant, which makes it ideal in many ways.1 The high activation energies in the reactions of oxygen require that catalysts be employed.2 In combination with molecular oxygen, the chemistry of copper catalysis increases exponentially since oxygen can act as either a sink for electrons (oxidase activity) and/or as a source of oxygen atoms that are incorporated into the product (oxygenase activity). The oxidation of copper with oxygen is a facile process allowing catalytic turnover in net oxidative processes and ready access to the higher CuIII oxidation state, which enables a range of powerful transformations including two-electron reductive elimination to CuI. Molecular oxygen is also not hampered by toxic byproducts, being either reduced to water, occasionally via H2O2 (oxidase activity) or incorporated into the target structure with high atom economy (oxygenase activity). Such oxidations using oxygen or air (21% oxygen) have been employed safely in numerous commodity chemical continuous and batch processes.3

However, batch reactors employing volatile hydrocarbon solvents require that oxygen concentrations be kept low in the head space (typically <5–11%) to avoid flammable mixtures, which can limit the oxygen concentration in the reaction mixture.4,5,6 A number of alternate approaches have been developed allowing oxidation chemistry to be used safely across a broader array of conditions. For example, use of carbon dioxide instead of nitrogen as a diluent leads to reduced flammability.5 Alternately, water can be added to moderate the flammability allowing even pure oxygen to be employed.6 New reactor designs also allow pure oxygen to be used instead of diluted oxygen by maintaining gas bubbles in the solvent, which greatly improves reaction rates and prevents the build up of higher concentrations of oxygen in the head space.4a,7 Supercritical carbon dioxide has been found to be advantageous as a solvent due its chemical inertness towards oxidizing agents and its complete miscibility with oxygen or air over a wide range of temperatures.8 An number of flow technologies9 including flow reactors,10 capillary flow reactors,11 microchannel/microstructure structure reactors,12 and membrane reactors13 limit the amount of or afford separation of hydrocarbon/oxygen vapor phase thereby reducing the potential for explosions.

Enzymatic oxidizing systems based upon copper that exploit the many advantages and unique aspects of copper as a catalyst and oxygen as an oxidant as described in the preceding paragraphs are well known. They represent a powerful set of catalysts able to direct beautiful redox chemistry in a highly site-selective and stereoselective manner on simple as well as highly functionalized molecules. This ability has inspired organic chemists to discover small molecule catalysts that can emulate such processes. In addition, copper has been recognized as a powerful catalyst in several industrial processes (e.g. phenol polymerization, Glaser-Hay alkyne coupling) stimulating the study of the fundamental reaction steps and the organometallic copper intermediates. These studies have inspiried the development of nonenzymatic copper catalysts. For these reasons, the study of copper catalysis using molecular oxygen has undergone explosive growth, from 30 citations per year in the 1980s to over 300 citations per year in the 2000s.

A number of elegant reviews on the subject of catalytic copper oxidation chemistry have appeared. Most recently, reviews provide selected coverage of copper catalysts14 or a discussion of their use in the aerobic functionalization of C–H bonds.15 Other recent reviews cover copper and other metal catalysts with a range of oxidants, including oxygen, but several reaction types are not covered.16 Several other works provide a valuable overview of earlier efforts in the field.17 This review comprehensively covers copper catalyzed oxidation chemistry using oxygen as the oxidant up through 2011. Stoichiometric reactions with copper are discussed, as necessary, to put the development of the catalytic processes in context. Mixed metal systems utilizing copper, such as palladium catalyzed Wacker processes, are not included here. Decomposition reactions involving copper/oxygen and model systems of copper enzymes are not discussed exhaustively. To facilitate analysis of the reactions under discussion, the current mechanistic hypothesis is provided for each reaction. As our understanding of the basic chemical steps involving copper improve, it is expected that many of these mechanisms will evolve accordingly.

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Aerobic Copper-Catalyzed Organic Reactions

This paper presents a review of catalytic ozonation and methods of enhancing molecular ozone reactions in water treatment. It is also an attempt to propose general ideas about mechanisms governing catalytic ozone reactions. Catalytic ozonation is a new means of contaminants removal from drinking water and wastewater. Its application is mainly limited to laboratory use. However, due to successful results further investigation is to be carried out. The majority of models proposed represent more of a speculative approach to the problem than a hypothesis based on experimental data. It is therefore useful to provide a summary of the accomplishments concerning catalytic ozonation and methods of enhancing molecular ozone reactions that were published so far. A survey of the application of several homo- and heterogeneous catalysts, their activity and the parameters influencing the efficiency of catalytic systems is presented here as a short overview, the aim of which is to raise awareness of possible new approaches to water purification.

Catalytic ozonation and methods of enhancing molecular ozone reactions in water treatment

The wet oxidation of organic compounds composed only of C, H, and O, dyes, amides, and water-soluble polymers is discussed to clarify the basic nature of this process. The reactivity of the organic compounds composed of C, H, and O, dyes, and some amides was correlated well with their carbon content in the molecule (C/MW) or carbon content in their skeletal structure (C/MW‘). This C/MW index can be applied to roughly estimate the behavior of wastewaters containing various organic compounds. Polymers are easily decomposed by the wet oxidation because they can undergo intramolecular hydrogen abstraction in the chain-propagation step. The biodegradability of polymers and amides was improved by wet oxidation treatment, indicating an asset of this process. The function of homogeneous copper salts and the effect of hydrogen peroxide are discussed. The action of Co/Bi composite oxide designed for the treatment of refractory carboxylic acids, Mn/Ce composite oxide for ammonia and other organic compounds, and Ru/C...

Catalytic and Noncatalytic Wet Oxidation

Addition of a small amount of cerium (3 and 5 mol.%) remarkably affected the oxidation state of manganese oxide. Manganese oxide without cerium absorbed oxygen in the temperature region from 600 to 900 K to form Mn2O3, while Mn2O3 was not formed in the presence of cerium. In the low temperature region (< 700 K) the valence of Mn was 3.2 in the presence of cerium while it was 2.85 in the absence of cerium. It was concluded that cerium provided oxygen to manganese oxide at low temperature and, on the contrary, withdrew oxygen at high temperatures. This behavior well explained the catalytic action of manganese-cerium composite oxide in the oxidation of CO and in the decomposition of N2O.

Effect of cerium on the mobility of oxygen on manganese oxides

Steam reforming of ethanol over CuO/CeO2 was studied. Acetaldehyde and hydrogen were mainly produced at 260degreesC. At 380degreesC, acetone was the main product, and 2 mol of hydrogen was produced from 1 mol of ethanol. The formation of hydrogen accompanied by the production of acetone was considered to proceed through the following, consecutive reactions: dehydrogenation of ethanol to acetaldehyde. aldol condensation of the acetaldehyde, and the reaction of the aldol with the lattice oxygen [O(s)] on the catalyst to form a surface intermediate, followed by its dehydrogenation and decarboxylation. The overall reaction was expressed by2C(2)H(5)OH + H2O --> CH3COCH3 + CO2 + 4H(2). Ceria played an important role as an oxygen supplier. The addition of MgO to CuO/CeO2 resulted in the production of hydrogen at lower temperatures by accelerating aldol condensation. (C) 2004 Elsevier B.V. All rights reserved.

Catalytic steam reforming of ethanol to produce hydrogen and acetone

Wet oxidation of ammonia catalyzed by cerium-based composite oxides

The activity of precious meta catalysts in the wet oxidation of organic compounds was investigated. Ruthenium was the most active catalyst among the precious metals examined, and cerium (IV) oxide was the most effective support. The Ru/Ce catalyst rivaled homogeneous copper catalyst, which is used in the practical wastewater treatment, for the oxidation of n-propyl alcohol, n-butyl alcohol, phenol, acetamide, poly (propylene glycol), and acetic acid. In addition, it was especially effective for the oxidation of some compounds with high oxygen content such as poly (ethylene glycol), ethylene glycol, formaldehyde, and formic acid.

Seiichiro Imamura

Papers

Catalytic and Noncatalytic Wet Oxidation

Effect of cerium on the mobility of oxygen on manganese oxides

Catalytic steam reforming of ethanol to produce hydrogen and acetone

Wet oxidation of ammonia catalyzed by cerium-based composite oxides

Wet oxidation catalyzed by ruthenium supported on cerium(IV) oxides