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

CeO2–Al2O3 mixed oxides with different CeO2 loading (in the range of 0.5–12 wt.%) were prepared by wetness impregnation of alumina with aqueous solution of di-ammonium hexanitrate cerate (NH4)2[Ce(NO3)6]. The samples after calcination at 773 and 1073 K were characterized by different techniques, using X-ray diffraction (XRD), UV–VIS diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR). It is shown that different types of cerium oxide species are formed on the surface depending on the amount of CeO2 and temperature of calcination of the samples. XRD showed the formation of nanocrystallites of ceria on alumina surface when the amount of CeO2 is higher than 6 wt.%; at lower concentrations ceria was found to be amorphous. The ceria loading lower than 6 wt.% stabilizes the textural properties of alumina. At loading of 1 wt.% of CeO2 XPS spectra reveals the presence of a strong interaction between ceria and alumina leading to a formation of superficial CeAlO3-like phase. TPR results show that well dispersed CeO2 particles present on the surface of alumina form CeAlO3 at temperature of reduction in the range of 873–993 K, while for the reduction of CeO2 crystallites, a higher temperature of reduction of 1190 K is needed.

Characterization of ceria-coated alumina carrier

Carbon formation and its influence on ethanol steam reforming over Ni/Al2O3 catalysts

Ni and Pt catalysts supported on α-Al2O3, α-Al2O3-ZrO2 and ZrO2 were studied in the dry reforming of methane to produce synthesis gas. All catalytic systems presented well activity levels with TOF (s−1) values between 1 and 3, being Ni based catalysts more active than Pt based catalysts. The selectivity measured at 650 °C, expressed by the molar ratio H2/CO reached values near to 1. Concerning stability, Pt/ZrO2, Pt/α-Al2O3-ZrO2 and Ni/α-Al2O3-ZrO2 systems clearly show lower deactivation levels than Ni/ZrO2 and Ni or Pt catalysts supported on α-Al2O3. The lowest deactivation levels observed in Ni and Pt supported on α-Al2O3-ZrO2, compared with Ni and Pt supported on α-Al2O3 can be explained by an inhibition of reactions leading to carbon deposition in systems having ZrO2. These results suggest that ZrO2 promotes the gasification of adsorbed intermediates, which are precursors of carbon formation and responsible for the main deactivation mechanism in dry reforming reaction.

Martin Schmal

Papers

Characterization of ceria-coated alumina carrier

Carbon formation and its influence on ethanol steam reforming over Ni/Al2O3 catalysts

Study of Ni and Pt catalysts supported on α-Al2O3 and ZrO2 applied in methane reforming with CO2

Reforming of Methane with Carbon Dioxide over Pt/ZrO2/Al2O3 Catalysts

Kinetics and reaction pathway of the CO2 reforming of methane on Rh supported on lanthanum-based solid