Optical Properties of Nanocrystalline Monoclinic Y2O3 Stabilized by Grain Size and Plastic Strain Effects via High-Pressure Torsion.

Yttrium oxide (yttria) with monoclinic structure exhibits unique optical properties; however, the monoclinic phase is thermodynamically stable only at pressures higher than ∼16 GPa. In this study, the effect of grain size and plastic strain on the stability of monoclinic phase is investigated by a high-pressure torsion (HPT) method. A cubic-to-monoclinic phase transition occurs at 6 GPa, which is ∼10 GPa below the theoretical transition pressure. Microstructure analysis shows that monoclinic phase forms in nanograins smaller than ∼22 nm and its fraction increases with plastic strain, while larger grains have a cubic structure. The band gap decreases and the photoluminescence features change from electric dipole to mainly magnetic dipole without significant decrease in the photoluminescence intensity after formation of the monoclinic phase. It is also suggested that monoclinic phase formation is due to the enhancement of effective internal pressure in nanograins.

Visible light active Bi3TaO7 nanosheets for water splitting.

Tantalate semiconductors are potential photocatalysts for hydrogen generation via photocatalytic water splitting reaction because the conduction band of tantalates is composed of the tantalum 5d orbital, which is located at a more negative potential than that of the H+/H2 half reaction, i.e., 0.0 V vs. NHE. Bi3TaO7 is a stable tantalate under acidic or alkaline conditions, with a band gap suitable for visible light absorption. However, the photocatalytic properties of Bi3TaO7 are only reported based on the dye degradation reactions, probably due to the fast electron/hole recombination losses. 2D crystal-like nanosheets with a thickness of a few nanometers show unique features such as high carrier mobility, the quantum Hall effect, high specific surface area, and excellent electrical/thermal conductivity. 2D structures can also enhance the photocatalytic properties because photo-generated charge carriers in nanosheets are less prone to fast recombinations as compared to their bulk counterparts. In this study, nanosheets of Bi3TaO7 are produced by a liquid exfoliation method and the photocatalytic hydrogen generation reaction is investigated for both the as-synthesized Bi3TaO7 nanoparticles and Bi3TaO7 nanosheets.

Chemical and thermal properties of VO2 mechanochemically derived from V2O5 by co-milling with paraffin wax.

A novel mechanochemical reduction process of V2O5 to VO2 was established by milling with paraffin wax (PW, average molecular weight 254-646), serving as a reductant. The reduction progressed with increasing milling time and mass ratio V2O5 : PW (MRVP). The mechanochemically derived VO2 became phase pure after milling for 3 h with an MRVP of 30 : 1 and exhibited a reversible polymorphic transformation between tetragonal and monoclinic phases at around 53-60 °C and 67-79 °C during heating and cooling, respectively. The latent heat was above 20 J g-1 in both processes, being superior to those of commercial VO2. Doping of starting V2O5 with Cr, Mo or W at 1 at% in the form of oxide did not increase the latent heat. This is another difference from the conventionally prepared doped VO2. These anomalous heat storage properties of mechanochemically derived VO2 were discussed mainly on the basis of X-ray photoelectron spectroscopy V2p3/2 peaks combined with ion etching. The observed relatively high heat storage capacity of undoped VO2 is primarily ascribed to the abundance of V4+ ionic states introduced during milling with PW, which were stabilized with simultaneously introduced structural degradation throughout the entire particles. The possible role of a remaining small amount of PW was also discussed.