Dedi Liu

High-pressure Raman scattering and x-ray diffraction of phase transitions in MOO3

The high-pressure behavior of molybdenum trioxides (MoO3) has been investigated by angle-dispersive synchrotron x-ray powder diffraction and Raman spectroscopy techniques in a diamond anvil cell up to 43 and 30 GPa, respectively. In the pressure range of up to 43 GPa, structural phase transitions from the orthorhombic α-MoO3 phase (Pbnm) to the monoclinic MoO3-II phase (P21/m), and then to the monoclinic MoO3-III phase (P21/c), occurred at pressures of about 12 and 25 GPa at room temperature, respectively. Our observation of the transition from the orthorhombic α-MoO3 to the monoclinic MoO3-II phase is in disagreement with earlier studies in which the phase transition could not be obtained when only pressure is applied. The changes in the Mo–O distances and O–Mo–O and Mo–O–Mo angles may explain the changes in Raman spectrum. The pressure dependence of the volume of two monoclinic high-pressure phases is described by a third-order Birch–Murnaghan equation of state, which yields a bulk modulus value of B0=1...

Synthesis and high pressure induced amorphization of C60 nanosheets

C60 nanosheets with thicknesses in the nanometer range were synthesized by a simple method. Compared to bulk C60, the lattice of the nanosheets is expanded by about 0.4%. In situ Raman spectroscopy and energy-dispersive x-ray diffraction under high pressures have been employed to study the structure of the nanosheets. The studies indicate that the bulk modulus of the C60 nanosheets is significantly larger than that of bulk C60. The C60 cages in nanosheets can persist at pressures over 30GPa, 3GPa higher than for bulk C60. These results suggest that C60 crystals in even small size will be a potential candidate of superhard materials.

Rotational dynamics of confined C60 from near-infrared Raman studies under high pressure.

Peapods present a model system for studying the properties of dimensionally constrained crystal structures, whose dynamical properties are very important. We have recently studied the rotational dynamics of C60 molecules confined inside single walled carbon nanotube (SWNT) by analyzing the intermediate frequency mode lattice vibrations using near-infrared Raman spectroscopy. The rotation of C60 was tuned to a known state by applying high pressure, at which condition C60 first forms dimers at low pressure and then forms a single-chain, nonrotating, polymer structure at high pressure. In the latter state the molecules form chains with a 2-fold symmetry. We propose that the C60 molecules in SWNT exhibit an unusual type of ratcheted rotation due to the interaction between C60 and SWNT in the “hexagon orientation,” and the characteristic vibrations of ratcheted rotation becomes more obvious with decreasing temperature.

High-Pressure Structural Transitions of Sc2O3 by X-ray Diffraction, Raman Spectra, and Ab Initio Calculations

The high-pressure behavior of scandium oxide (Sc(2)O(3)) has been investigated by angle-dispersive synchrotron powder X-ray diffraction and Raman spectroscopy techniques in a diamond anvil cell up to 46.2 and 42 GPa, respectively. An irreversible structural transformation of Sc(2)O(3) from the cubic phase to a monoclinic high-pressure phase was observed at 36 GPa. Subsequent ab initio calculations for Sc(2)O(3) predicted the phase transition from the cubic to monoclinic phase but at a much lower pressure. The same calculations predicted a second phase transition at 77 GPa from the monoclinic to hexagonal phase.

Reversible Polymerization in Doped Fullerides Under Pressure: The Case Of C60(Fe(C5H5)2)2

High-pressure Raman studies have been carried out on single crystalline C(60)(Fc)(2) nanosheets up to 25.4 GPa. Our results show that the charge transfer between Fc (ferrocene) and C(60) increases in the low-pressure range. Above 5 GPa, C(60) molecules start to form a chainlike polymer structure, and this polymerization is reversible upon decompression, in contrast to that of pristine C(60). The special layered structure of C(60)(Fc)(2) restricts the polymerization of C(60) molecules in some directions and explains the formation of the linear chainlike polymeric structure of the C(60) lattice under pressure. We suggest that the reversible polymerization is related to the increased charge transfer and the overridden steric repulsion of counterions.

Simple synthesis and luminescence characteristics of PVP-capped GeO 2 nanoparticles

Polyvinylpyrrolidone (PVP)-capped rutile GeO2 nanoparticles were synthesized through a facile hydrothermal process. The obtained nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), thermo gravimetric analysis (TGA), and photoluminescence spectroscopy (PL). The capped GeO2 nanoparticles showed significantly enhanced luminescence properties compared with those of the uncapped ones. We attributed this result to the effect of reducing surface defects and enhancing the possibility of electron-hole recombination of the GeO2 nanoparticles by the PVPmolecules. PVP-capped GeO2 nanoparticles have potential application in optical and electronic fields.

High pressure and high temperature induced polymerization of C60 nanotubes

C60 nanotubes with outer diameters ranging from 400–800 nm were polymerized at 1.5 GPa, 573 K and 2.0 GPa, 700 K, respectively. Raman and photoluminescence spectroscopy were employed to characterize the polymeric phases of the treated samples. Both Raman and photoluminescence spectra showed that the C60 nanotubes transformed into the dimer and orthorhombic phases under the two different conditions, respectively. The photoluminescence peaks were tuned from visible to near infrared range. Comparative studies indicated that C60 nanotubes were more difficult to polymerize than bulk C60 material under the same conditions due to the nanoscale size effect in the C60 nanotubes.

Photoluminescence properties of high-pressure-polymerized C60 nanorods in the orthorhombic and tetragonal phases

C60 nanorods in two polymeric phases have been synthesized under different high pressure and high temperature conditions. Orthorhombic and tetragonal phases have been identified from Raman spectra. The rod shape can be kept under quasihydrostatic pressure. The photoluminescence intensity of the polymeric C60 nanorods has been greatly enhanced compared with that of pristine C60 nanorods. The main fluorescence band shifted from 730nm in the unpolymeric phase to 748nm and near infrared 780nm in the orthorhombic and tetragonal phases, respectively. The enhanced photoluminescence with tunable frequency for different polymeric C60 nanorods suggests potential applications in luminescent nanomaterials.

Comparative studies of structural transition between AIN nanocrystals and nanowires

The structural transition of AIN nanocrystals and nanowires were investigated simultaneously under pressures up to 37.2 GPa by in situ angle dispersive high-pressure x-ray diffraction using synchrotron radiation source and a single diamond anvil cell. The size of hexagonal AIN nanocrystals and the diameter of nanowires are 45 nm on average. A pressure-induced wurtzite to rocksalt phase transition starts at 21.5 GPa and completes at 27.8 GPa for the nanocrystals and nanowires, respectively. The high-pressure behaviors of AlN nanocrystals the same as the AIN nanowires might arise from the similar size and diameter in nanocrystals and nanowires. Hexagonal AIN nanocrystals (45 nm) display an apparent volumetric contraction as compared to the AlN nanocrystals (10 nm) which might induce the difference of transition pressure.

Insertion of N2 into the Channels of AFI Zeolite under High Pressure.

We present an experimental study of a new hybrid material where nitrogen is encapsulated in the channels of porous zeolite AlPO4-5 (AFI) single crystals by a high-pressure method. The high-pressure behavior of nitrogen confined inside the AFI nano-channels is then investigated by Raman spectroscopy up to 44 GPa. Under pressure, the Raman modes of confined nitrogen show behaviors different from those of the bulk nitrogen. After the return to atmospheric pressure, it is demonstrated that non-gaseous nitrogen can be effectively stabilized by being confined inside the intact AFI sample. This result provides new insight into nitrogen capture and storage technologies.