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

Interest in catalysis by metal nanoparticles (NPs) is increasing dramatically, as reflected by the large number of publications in the last five years. This field, "semi-heterogeneous catalysis", is at the frontier between homogeneous and heterogeneous catalysis, and progress has been made in the efficiency and selectivity of reactions and recovery and recyclability of the catalytic materials. Usually NP catalysts are prepared from a metal salt, a reducing agent, and a stabilizer and are supported on an oxide, charcoal, or a zeolite. Besides the polymers and oxides that used to be employed as standard, innovative stabilizers, media, and supports have appeared, such as dendrimers, specific ligands, ionic liquids, surfactants, membranes, carbon nanotubes, and a variety of oxides. Ligand-free procedures have provided remarkable results with extremely low metal loading. The Review presents the recent developments and the use of NP catalysis in organic synthesis, for example, in hydrogenation and C--C coupling reactions, and the heterogeneous oxidation of CO on gold NPs.

Nanoparticles as Recyclable Catalysts: The Frontier between Homogeneous and Heterogeneous Catalysis

In this chapter, we will restrict our attention to the ferrites and a few other closely related materials. The great interest in ferrites stems from their unique combination of a spontaneous magnetization and a high electrical resistivity. The observed magnetization results from the difference in the magnetizations of two non-equivalent sub-lattices of the magnetic ions in the crystal structure. Materials of this type should strictly be designated as “ferrimagnetic” and in some respects are more closely related to anti-ferromagnetic substances than they are to ferromagnetics in which the magnetization results from the parallel alignment of all the magnetic moments present. We shall not adhere to this special nomenclature except to emphasize effects, which are due to the existence of the sub-lattices.

Ferromagnetic materials

Advances in the development of novel cobalt Fischer-Tropsch catalysts for synthesis of long-chain hydrocarbons and clean fuels.

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

Silver supported catalysts on alpha-alumina were prepared and characterized by Brunauer-Emmet-Teller equations, scanning electronic microscopy, X-ray diffraction and atomic force microscopy techniques. Results show that these are powerful techniques for the determination of texture, morphology and surface properties. It has been shown that the addition of Cs in the Ag/Al2O3 catalyst increased the dispersion of silver with the formation of small silver particles over a thin silver film already formed over the alumina support. It is important to stress that atomic force microscopy measurements are significant to observe the film and the dispersion of Ag and, on the contrary, X-ray photoelectronic spectroscopy did not, however, it allows to the conclusion that undistinguishable silver, either as metallic or oxidation state, are present at the surface. X-ray diffraction results confirm predominantly metallic silver.

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The promoting effect of cesium on structure and morphology of silver catalysts

There is a high industrial demand for MMA and DMA, however, the production of TMA is favored with the commercial catalysts. This work tested the methanol amination reaction with HZSM-5 and Cu/HZSM-5 zeolites (%Cu = 1.2, 3.7 and 6.0). Regarding the MMA selectivity, light differences were observed among Cu/HZSM-5 catalysts and pure zeolite, although the catalysts containing 3.7% copper was slightly more selective to MMA than the other metallic catalysts studied. From these results it is suggested that the metal loading present in the catalysts leads to a modification in the nature of the acidic sites, in particular, the selectivity depends on ratio Bronsted/Lewis acid sites. This modifications would facilitate the amines desorption during the reaction.

The Influence of the Acid Sites on the Methylamines Synthesis with Cu-HZSM-5 Zeolite

Surface Analyses of adsorbed and deposited species on the Ni-Mo catalysts surfaces after Guaiacol HDO. Influence of the alumina and SBA-15 supports.

Oxidative coupling of methane was investigated on Na/CaO and Ce/Na/CaO catalysts with different sodium and cerium contents. The reaction was carried out in a micro fixed-bed flow reactor operating at atmospheric pressure, at 700 and 750°C and molar ratio feed of CH4 : O2 : N2 = 50 : 10 : 40. Catalysts were compared at isoconversion and were characterized by BET, XRD and XPS. The addition of cerium to Na/CaO catalyst increased the specific activity by a factor of eight. These catalytic and characterization results were related to the presence not only of Na+O- active sites, formed by the introduction of Na+ in the CaO lattice, but also to peroxide active sites. A mechanism is proposed to explain the role of cerium in increasing the rate of the regeneration step of the O
 s
 –
 and Na2O2 sites.

Martin Schmal

Papers

The promoting effect of cesium on structure and morphology of silver catalysts

The Influence of the Acid Sites on the Methylamines Synthesis with Cu-HZSM-5 Zeolite

Surface Analyses of adsorbed and deposited species on the Ni-Mo catalysts surfaces after Guaiacol HDO. Influence of the alumina and SBA-15 supports.

Oxidative coupling of methane on Ce/Na/CaO catalysts

NO reduction with acetaldehyde on alumina-supported Pd-Mo catalysts