Single-crystalline and uniform nanopolyhedra, nanorods, and nanocubes of cubic CeO2 were selectively prepared by a hydrothermal method at temperatures in the range of 100-180 degrees C under different NaOH concentrations, using Ce(NO3)3 as the cerium source. According to high-resolution transmission electron microscopy, they have different exposed crystal planes: {111} and {100} for polyhedra, {110} and {100} for rods, and {100} for cubes. During the synthesis, the formation of hexagonal Ce(OH)3 intermediate species and their transformation into CeO2 at elevated temperature, together with the base concentration, have been demonstrated as the key factors responsible for the shape evolution. Oxygen storage capacity (OSC) measurements at 400 degrees C revealed that the oxygen storage takes place both at the surface and in the bulk for the as-obtained CeO2 nanorods and nanocubes, but is restricted at the surface for the nanopolyhedra just like the bulk one, because the {100}/{110}-dominated surface structures are more reactive for CO oxidation than the {111}-dominated one. This result suggests that high OSC materials might be designed and obtained by shape-selective synthetic strategy.

Shape-selective synthesis and oxygen storage behavior of ceria nanopolyhedra, nanorods, and nanocubes.

The controllable synthesis of nanostructured CeO2-based materials is an imperative issue for environment- and energy-related applications. In this review, we present the recent technological and theoretical advances related to the CeO2-based nanomaterials, with a focus on the synthesis from one dimensional to mesoporous ceria as well as the properties from defect chemistry to nano-size effects. Seven extensively studied aspects regarding the applications of nanostructured ceria-based materials are selectively surveyed as well. New experimental approaches have been demonstrated with an atomic scale resolution characterization. Density functional theory (DFT) calculations can provide insight into the rational design of highly reactive catalysts and understanding of the interactions between the noble metal and ceria support. Achieving desired morphologies with designed crystal facets and oxygen vacancy clusters in ceria via controlled synthesis process is quite important for highly active catalysts. Finally, remarks on the challenges and perspectives on this exciting field are proposed.

Nanostructured ceria-based materials: synthesis, properties, and applications

The Binary Rare Earth Oxides.

Blue shifts corresponding to the absorption edge in the UV-A (310–400 nm) range are obtained from ultraviolet (UV) absorption spectra of monodisperse CeO2−x (0<x<0.5) nanoparticles, which are produced as toluene suspensions by a successive microemulsification method. The blue shift of the nanoparticles is inversely proportional to the 2.2 power of the particle size for a direct transition, but no relation is found for an indirect transition. In contrast, the shift for thin films of 100–200 nm thickness exhibits a relation nearly inverse proportional to the square root of the thickness for the direct transition. These relations are different from that for the quantum size effect, though the difference is small for the nanoparticles. A possible explanation for the blue shift is a valence change of the Ce ions.

Blue shift in ultraviolet absorption spectra of monodisperse CeO2−x nanoparticles

Spherical cerium oxide nanoparticles and microsized rod-shaped and spindle-like CeO2 structures have been synthesized using a polyol method. When the duration of reaction and the concentration of cerium precursor are controlled, CeO2 products of different morphologies can be selectively produced. Results from XRD, XPS, SEM, and FT-IR measurements suggest that the CeO2 nanospheres are formed from the decomposition of the cerium precursor. Further reactions between the as-prepared CeO2 and ethylene glycol yield the rods/spindle-like cerium formate particles. These morphologies are preserved even after calcination. The order of band gap energy of these samples was found to be rod-shaped > spherical > spindle-like samples, as determined by the UV−Vis spectroscopic method. Compared to a nonoriented polycrystalline CeO2, these samples show an increase in band gap energy due to the quantum size effect. The higher catalytic activity on CO conversion in a spindle-like sample can be explained from the extent of Ce(...

Morphology-Controllable Synthesis of Mesoporous CeO2 Nano- and Microstructures

Cerium(IV) oxide ultrafine particles were prepared using a reaction within reversed micelles, which was known as a microemulsion method. The ultrafine particles, which were obtained by mixing the water-in-oil microemulsions containing cerium nitrate solution with those of ammonium hydroxide, were characterized by high-resolution electron microscope (HREM) observations. HREM micrographs revealed that nanometer-sized CeO2 particles were formed, and their shapes were uniform. Selected-area electron diffraction patterns of the particles were completely indexed as those of cerium(IV) oxide with the cubic fluorite structure, and the lattice constant calculated from radii of Debye−Sherrer rings was 0.541 nm. Most of the particles were distributed between 2 and 6 nm, and the mean particle size obtained in this method was between 2.6 and 4.1 nm. The size of 2.6 nm is the smallest among the values ever reported for CeO2 particles. Both direct and indirect optical energy gaps of the particles were independent of the...

Takao Sakata and

Papers

Characterization of Cerium(IV) Oxide Ultrafine Particles Prepared Using Reversed Micelles