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 is a catalytic material of exceptional technological importance, and the precise role of oxygen vacancies is crucial to the greater understanding of these oxide materials. In this work, two ceria nanorod samples with different types and distributions of oxygen vacancies were synthesized. A direct relationship between the concentration of the larger size oxygen vacancy clusters and the reducibility/reactivity of nanosized ceria was revealed. These results may be an important step in understanding and designing active sites at the surface of metal oxide catalytic materials.

Oxygen Vacancy Clusters Promoting Reducibility and Activity of Ceria Nanorods

Defect sites play an essential role in ceria catalysis. In this study, ceria nanocrystals with well-defined surface planes have been synthesized and utilized for studying defect sites with both Raman spectroscopy and O2 adsorption. Ceria nanorods ({110} + {100}), nanocubes ({100}), and nano-octahedra ({111}) are employed to analyze the quantity and quality of defect sites on different ceria surfaces. On oxidized surfaces, nanorods have the most abundant intrinsic defect sites, followed by nanocubes and nano-octahedra. When reduced, the induced defect sites are more clustered on nanorods than on nanocubes, although similar amounts (based on surface area) of such defect sites are produced on the two surfaces. Very few defect sites can be generated on the nano-octahedra due to the least reducibility. These differences can be rationalized by the crystallographic surface terminations of the ceria nanocrystals. The different defect sites on these nanocrystals lead to the adsorption of different surface dioxygen...

Probing defect sites on CeO2 nanocrystals with well-defined surface planes by Raman spectroscopy and O2 adsorption.

The water–gas shift (WGS) reaction (CO+H2OQCO2+H2) plays an important role in fuel processing for polymer electrolyte membrane (PEM) fuel-cell applications. The hydrogen in the reformate gas is upgraded by removal of the carbon monoxide, which is a strong poison of the anode catalysts in current PEM fuel cells. Active shift catalysts that are also stable under the operating conditions of practical fuel-cell systems are under intense study, and nanostructured Au-CeO2, first reported by Fu et al. as a promising lowtemperature shift catalyst, holds a prominent position. This catalyst exploits the strong interaction of ceria with finely dispersed and stabilized gold atoms and clusters on the surface of ceria. Gold nanoparticles and clusters that interact strongly with oxide supports were first described by Haruta et al. to be extremely active CO oxidation catalysts. Numerous studies since then have reaffirmed the activity of well-dispersed gold for CO oxidation and many other reactions. While a full mechanism of this catalytic process still needs to be established, even for the simplest of these reactions (CO oxidation), a careful investigation of the reported strong metal–support interaction through structural studies may provide further mechanistic insights as well as rationalize the design of practical catalysts. For the WGS reaction on Au-CeO2, the importance of nanoscale ceria as a support that stabilizes active gold species has been demonstrated recently. Hydrolysis methods for the synthesis of ceria nanocrystals have proven to be powerful for controlling particle size and crystal shape. For example, Yan et al. have obtained single-crystalline CeO2 nanopolyhedra ({111} and {100}), nanorods ({110} and {100}), and nanocubes ({100}) by hydrolysis of cerium(III) salts, combined with a hydrothermal treatment, and have further found that oxygen storage takes place both at the surface and in the bulk for nanorods and nanocubes but is restricted to the surface for nanopolyhedra, just like its bulk ceria counterpart. Trovarelli et al. have studied the rearrangement of CeO2 crystallites under airaging and the exposure of more reactive {100} surfaces for CO oxidation. Very little is known for Au-CeO2 composite polycrystalline nanomaterials with respect to the shape/crystal plane effect of CeO2 on the gold species< activity/stabilization as highly active catalysts for the WGS reaction. Herein, we present activity correlations with the shape (rod, cube, polyhedron) and crystal plane of nanoscale ceria as a support for gold catalysts for this reaction. The interaction between deposited gold and different crystal orientations is investigated at ambient pressure andmonitored by several analytical techniques, including transmission electron microscopy (TEM), high-resolution TEM (HRTEM), X-ray photoelectron spectroscopy (XPS), and temperature-programmed reduction by hydrogen (H2-TPR). Figure 1 depicts our two-step preparation process, which includes hydrothermal synthesis of ceria nanorods, nano-

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Shape and Crystal-Plane Effects of Nanoscale Ceria on the Activity of Au-CeO2 Catalysts for the Water–Gas Shift Reaction†

The article discusses oxidation catalysis by substitutional cation doping of binary oxides. Substitutional cation doping is not the only possibility. One can imagine that replacing some anions with other anions may also be beneficial. There is evidence that the presence of small amounts of halogen in the feed or on the oxide surface improves its catalytic activity. It is very likely that doped oxide catalysts have been used before the concept was formulated explicitly. Most oxide catalysts have low levels of impurities that may be substitutional dopants. If they segregate at the surface, they can affect the catalytic activity without our knowledge even though their net concentration is very low. It is also possible that the 'as-prepared' catalyst is a doped oxide that, under reducing reaction conditions, is converted to very small metallic dopant clusters supported on the host oxide. The physical and chemical properties of such clusters are different from those of a bulk metal, and it is difficult to distinguish them from a doped oxide.

Catalysis by doped oxides.

Insights into the redox properties of ceria-based oxides and their implications in catalysis

In this study, a series of conventional polycrystalline ceria and single-crystalline ceria nanorods and nanocubes were prepared by hydrothermal methods, and their structural, redox, and morphological properties were investigated using XRD, SEM, HRTEM, BET, temperature-programmed reduction, and oxygen storage capacity measurements. According to HRTEM, they are characterized by exposure of different surfaces: {100} surface for nanocubes; {100}, {110}, and in part {111} for nanorods; and mainly {111} for conventional polycrystalline ceria, with a morphology dominated by {111}-enclosed octahedral particles. The presence of more-reactive exposed surfaces affects the reaction of soot oxidation positively, with an increase in activity in nanoshaped materials compared with conventional ceria. Thermal aging, although detrimental for surface area, is shown to affect morphology by promoting irregular truncation of edges and corners and development of more reactive surface combinations in all crystal shapes. It is li...

Eleonora Aneggi

Papers

Insights into the redox properties of ceria-based oxides and their implications in catalysis

Shape-Dependent Activity of Ceria in Soot Combustion

Promotional effect of rare earths and transition metals in the combustion of diesel soot over CeO2 and CeO2–ZrO2

Surface-structure sensitivity of CO oxidation over polycrystalline ceria powders

BMP tests of source selected OFMSW to evaluate anaerobic codigestion with sewage sludge