Gimyeong Seong

Green solvent for green materials: a supercritical hydrothermal method and shape-controlled synthesis of Cr-doped CeO2 nanoparticles.

This paper describes a supercritical hydrothermal synthesis method as a green solvent process, along with products based on this method that can be used as green materials that contribute to solving environmental problems. The first part of this paper summarizes the basics of this method, including the mechanism of the reactions, specific features of the supercritical state for nanoparticle synthesis, the continuous flow-type reactor and applications; this provides a better understanding of the suitability of this method to synthesize green materials. The second part of the paper describes the method used to synthesize Cr-doped CeO2 nanoparticles, which show an extremely high oxygen storage capacity, suggesting their high potential as an environmental catalyst. Transmission electron microscopy and scanning electron microscope images showed octahedral Cr-doped CeO2 nanoparticles with sizes of 15–30 nm and cubic Cr-doped CeO2 nanoparticles with sizes of 5–8 nm. Octahedral Cr-doped CeO2 nanoparticles exposing (111) facets and cubic Cr-doped CeO2 nanoparticles exposing (100) facets were determined by high-resolution transmission electron microscopy and selected area electron diffraction. The X-ray diffraction peaks shifted to a high angle because the radius of the Cr ion is smaller than that of the Ce ion.

Atomic-Scale Valence State Distribution inside Ultrafine CeO2 Nanocubes and Its Size Dependence

Atomic-scale analysis of the cation valence state distribution will help to understand intrinsic features of oxygen vacancies (VO ) inside metal oxide nanocrystals, which, however, remains a great challenge. In this work, the distribution of cerium valence states across the ultrafine CeO2 nanocubes (NCs) perpendicular to the {100} exposed facet is investigated layer-by-layer using state-of-the-art scanning transmission electron microscopy-electron energy loss spectroscopy. The effect of size on the distribution of Ce valence states inside CeO2 NCs is demonstrated as the size changed from 11.8 to 5.4 nm, showing that a large number of Ce3+ cations exist not only in the surface layers, but also in the center layers of smaller CeO2 NCs, which is in contrast to those in larger NCs. Combining with the atomic-scale analysis of the local structure inside the CeO2 NCs and theoretical calculation on the VO forming energy, the mechanism of size effect on the Ce valence states distribution and lattice expansion are elaborated: nano-size effect induces the overall lattice expansion as the size decreased to ≈5 nm; the expanded lattice facilitates the formation of VO due to the lower formation energy required for the smaller size, which, in principle, provides a fundamental understanding of the formation and distribution of Ce3+ inside ultrafine CeO2 NCs.