Calculated Vibrational Frequencies of PMo12O40 3- and its Fragments

Calculated vibrational frequencies are reported for the PMo₁₂O₄₀ ^3– ion according to a 53-atomic tetrahedral model (T_d). The results are compared with calculated frequencies for fragments of this structure, viz. PO₄ (T_d), Mo₃O₁₃ (C_3v), Mo₃O₇ (C_3v, Mo₂O₁₁ (C_s) and Mo₂O₁₀ (C_s).

A complete vibrational analysis of the PMo₁₂O₄₀ ^3– ion has been performed. The adopted model of T_d symmetry is an idealization of x-ray structure data. 1 The normal modes of vibration according to this model are distributed as:     

Surface Acidity of H-Birnessite: Infrared Spectroscopic Study of Formic Acid Decomposition

This paper presents the adsorption and thermal decomposition mechanism of formic acid on an H-birnessite sample. Changes in the surface and structure were characterized using infrared spectroscopy, N₂ gas adsorption–desorption, and thermal analysis techniques. The acid sites of H-birnessite were investigated by infrared and thermal analysis using pyridine as a molecular probe. Decomposition of formic acid started on H-birnessite at 120°C and was complete at 400°C. Infrared spectra revealed that the molecularly adsorbed formic acid species were transformed to a formate species, and the formate species were transformed to CO. The most stable adsorption structure for formic acid was found as a molecular monodentate configuration.     

Fiber Optic Spectrophotometer for Noninvasive Transmission and Diffuse Reflection Studies

We describe the construction of a simple but versatile single-beam spectrophotometer that uses no sample holder at all; one arm of a bifurcated fiber optic bundle illuminates the specimen, while the other receives the remitted light. Though designed with an eye to recording the diffuse reflection spectra of scattering-and-absorbing substances, it can also be used for conventional studies (ie transmission spectroscopy) by merely placing a plane mirror behind the cuvette. The performance of the instrument is evaluated and representative spectra of several powders, solutions, and biomaterials are presented.     

Vibrational modes of the stibine molecule

In this paper, we use the algebraic approach to describe the vibrational modes of stibine molecule (of C_3v molecular symmetry group) up to 21 quanta. As the stibine molecule exhibits stretch-bend resonances, we build an algebraic pyramidal coupling operator between stretching modes and bending modes adapted to this molecule. The standard deviation associated to the fit of the vibrational levels is 1.75 cm⁻¹.     

Multi-scale theoretical study of support effect on sintering dynamics of Pt

The capability of theoretical durability studies to offer an efficient alternative methodology for predicting the potential performance of catalysts has improved in recent years. In this regard, multi-scale theoretical methods for predicting sintering behavior of Pt on various catalyst supports are being developed. Various types of Pt diffusions depending on support were confirmed by the micro-scale ultra accelerated quantum chemical molecular dynamics (UA-QCMD) method. Moreover, macro-scale sintering behavior of Pt/γ-Al₂O₃, Pt/ZrO₂ and Pt/CeO₂ catalysts were studied using a developed 3D sintering simulator. Experimental results were well reproduced. While Pt on γ-Al₂O₃ sintered significantly, Pt on ZrO₂ sintered slightly and Pt on CeO₂ demonstrated the highest stability against sintering.     

Spectroscopic studies of interfacial structures of CeO2-TiO2 mixed oxides

We have investigated the geometric and electronic structures of the cerium oxide (CeO₂)-titanium dioxide (TiO₂) mixed oxides with various Ce/TiO₂ weight ratios prepared by the sol-gel method in detail by means of X-ray diffraction (XRD), high-resolution X-ray photoelectron spectroscopy (XPS), Raman spectroscopy excited by 325 and 514.5 nm lasers, and scanning electron microscope (SEM). Existence of cerium effectively inhibits the phase transition of TiO₂ from the anatase phase to the rutile phase. XRD peaks of TiO₂ anatase attenuate continuously with the increasing amount of CeO₂ in the mixed oxide, but the XRD peaks of cubic CeO₂ appear only after the weight ratio of Ce/TiO₂ reaches 0.50. The average crystalline sizes of TiO₂ anatase and cubic CeO₂ in CeO₂-TiO₂ mixed oxides are smaller than those in the corresponding individual TiO₂ anatase and cubic CeO₂. Raman spectroscopy excited by the 514.5 nm laser detects CeO₂ after the weight ratio of Ce/TiO₂ reaches 0.70 whereas Raman spectroscopy excited by the 325 nm laser detects CeO₂ after the weight ratio of Ce/TiO₂ reaches 0.90. XPS results demonstrate that Ti exists in the form of Ti⁴⁺ in the CeO₂-TiO₂ mixed oxide. Ce is completely in the form of Ce³⁺ in the mixed oxides with a 0.05 weight ratio of Ce/TiO₂. With the increasing weight ratio of Ce/TiO₂, Ce⁴⁺ dominates. On basis of these results, we proposed that CeO₂ initially nucleates at the defects (oxygen vacancies) within TiO₂ anatase, forming an interface bridged with oxygen between CeO₂ and TiO₂ anatase. At the interface, Ce species cannot substitute Ti⁴⁺ in the lattice of TiO₂ anatase whereas Ti⁴⁺ can substitute Ce⁴⁺ in the lattice of cubic CeO₂. The decreasing concentration of oxygen vacancies, the Ti-O-Ce interface, and the decreasing average crystalline size of TiO₂ anatase act to inhibit the phase transformation of TiO₂ anatase. With the increasing amounts of CeO₂, the CeO₂ clusters continuously grow and form cubic CeO₂ nanocrystals. Spectroscopic results strongly demonstrate that the surface region of CeO₂-TiO₂ mixed oxide is enriched with TiO₂.     

Investigation of monolayer dispersion of MoO3 supported on titanate nanotubes

The monolayer dispersion of MoO₃ supported on the surface of titanate nanotubes (TNT) were prepared by heating mechanical mixture of molybdate (HMA) and TNT. The result shows that MoO₃ can disperse spontaneously onto the surface of TNT, and the dispersion capacity is ca. 27 mg MoO₃/g TNT by X-ray diffraction (XRD). On the basis of thermogravimetric (TG) and X-ray photoelectron spectroscopy (XPS) analysis, it was found that the HMA as precursor could not decompose completely into MoO₃ crystal on the surface of TNT around the threshold above decomposed temperature due to the strong interaction between HMA and the surface of TNT.     

CH3OH/TiO2(110)界面的光电子能谱研究

Methanol/TiO₂(110) is a model system in the surface science study of photocatalysis where methanol is taken as a hole capture. However, the highest occupied molecular orbital of adsorbed methanol lies below the valence band maximum of TiO₂, preventing the hole transfer. To study the level alignment of this system, electronic structure of methanol covered TiO₂(110) surface has been measured by ultraviolet photoelectron spectroscopy and the molecular orbitals of adsorbed methanol have been clearly identified. The results indicate the weak interaction between methanol and TiO₂ substrate. The static electronic structure also suggests the mismatch of the energy levels. These static experiments have been performed without band gap excitation which is the prerequisite of a photocatalytic process. Future study of the transient electronic structure using time-resolved UPS has also been discussed.     

Effects of oxygen vacancies on the room-temperature ferromagnetism of Co-doped polycrystalline CeO2

Pure and Co-doped single-phase CeO₂ crystals were synthesized by a solid-state reaction method. Samples of different oxygen vacancy concentration were studied, including (1) as-sintered crystals, (2) powders ground from the same crystal, and (3) a cold-pressed pellet from the ground powder that was unannealed and annealed at 800 °C. By analyzing the magnetic behaviors, surface/volume ratio and O vacancy concentration, the effects of oxygen vacancies on the room-temperature ferromagnetism (RT-FM) of Co-doped CeO₂ were systematically investigated. The results confirm that the RT-FM observed in Co-doped CeO₂ has a direct relationship with the oxygen vacancy concentration, and support the oxygen vacancy mediated FM mechanism.     

Temperature-Dependent Raman Study on Vibrational Modes in LiTaO3

In this paper the results of temperature-dependent Raman study on the vibrational modes in LiTaO₃ crystals are presented. It is found that the two low-frequency A₁ modes show significant changes during the temperature changing process. “Modes softening” and “frequency-repulsion” effect was observed and dicussed.     

Effect of temperature of annealing on optical, structural and electrochromic properties of sol-gel dip coated molybdenum oxide films

The sol-gel dip-coating method is used for the preparation of MoO₃ thin films. The 6 layered MoO₃ films were prepared and annealed at various temperatures in the range of 200-350 °C. The band gap value for MoO₃ films were calculated from optical absorption measurements and it is in the range of 3.55-3.73 eV. XRD spectrum reveals (0 2 0) is the major diffraction plane for the films prepared above 250 °C, which reveals the formation of MoO₃ in α-orthorhombic phase. The films prepared at 200 °C and 250 °C exhibits amorphous nature. The FTIR spectrum confirms the presence of Mo-O-Mo and MoO bonds. Nanorods were observed in the SEM images in the case of MoO₃ films prepared above 250 °C. The films prepared at 250 °C exhibit maximum anodic diffusion coefficient of 9.61 × 10⁻¹¹ cm²/s. The same film exhibits the change in optical transmission of 58.4% at 630 nm with the optical density of 0.80.     

Theoretical study of the new compound VO2 (D)

The structural feature and the electronic properties of the newly synthesized compound VO₂ (D) are theoretically studied. Our calculations reveal that all of the V ions in VO₂ (D) form two types of chains. One of the chains contributes to the electronic states near the Fermi level, but the other one almost does not yet. Such discrepancy is attributed to the different strength of the VO bonds belonging to the different chains. Furthermore, it is found that one type of the VV chains characters the antiferromagnetic feature, whereas the other one is almost non-magnetic. So, the compound VO₂ (D) is of one-dimensional antiferromagnetic ordering. In addition, we propose that the structural transition from VO₂ (D) to the rutile-type VO₂ (R) is driven by three vibrational modes. The transition temperature is estimated to be about 600 K, being consistent with experiment.     

Preparation and photocatalytic property of CeO2 lamellar

A novel room temperature solid-state chemical synthesis was introduced to successfully fabricate CeO₂ samples, coupled by a polyethylene glycol 400 (PEG 400)/cetyl trimethylammonium bromide (CTAB)/sodium dodecyl sulfate (SDS). The as-prepared products were characterized by XRD, TEM, SEM, BET and UV. A study of photocatalytic degradation of the methylene blue MB under UV illumination has been carried out. It is indicated that the samples exhibit excellent photocatalytic activity. Besides, the samples assisted with surfactants possess higher photocatalytic activity than the sample without any surfactants, wherein the sample with SDS as an additive shows the highest photocatalytic activity, which is able to reach 89.6% MB degradation ratio within 60 min illumination. Moreover, the effects of important operational parameters such as initial MB concentration, catalyst loading and pH were also investigated. The above sample under the optimum conditions obtained the maximum MB degradation ratio up to 96.5%, which is higher than that of the commercial TiO₂ P25 under the same conditions. It can be concluded that CeO₂ will be a potential photocatalyst in the application of organic pollutant.     

Spectroscopic characterization of Yb:Sc2O3 transparent ceramics

Yb：Sc2O3 transparent ceramics are fabricated by a conventional ceramic process and sintering in H2 atmosphere. The room-temperature spectroscopic properties are investigated, and the Raman spectrum shows an obvious vibration characteristic band centred at 415 cm-1. There are three broad absorption bands around 891, 937, and 971 nm, respectively. The strongest emission peak is centred at 1.04 μm with a broad bandwidth （11 nm） and an emission cross-section of 1.8×10^-20 cm^2. The gain coefficient implies a possible laser ability in a range from 990 nm to 1425 nm. The energy-level structure shows that Yb：Sc2O3 ceramics have large Stark splitting at the ground state level due to their strong crystal field. All the results show that Yb：Sc2O3 transparent ceramics are a promising material for short pulse lasers.     

Assessment of damage ranges by measurements of the refractive index in ion implanted LiNbO3 and LiTaO3

Ion implantation in LiNbO₃ and LiTaO₃ produces radiation damage by nuclear collisions. The amorphisation of the lattice reduces the refractive index of the material. In the case of fast ion bombardment with helium this damage layer is buried below the surface. The refractive index profile which then exists is suitable for an optical waveguide on the surface which supports several modes. Analysis of the refractive index profile yields the damage distribution in the crystal and this in turn can be compared with theoretical estimates of the damage production and ion ranges.

Our analyses show that in the high energy range from 0.5 to 2.0 MeV the depth of the damage is predominantly controlled by the electronic stopping.     

The effects of Cr-doping on the room temperature ferromagnetism of chemically synthesized CeO2−δ nanoparticles

We report an investigation of the nature of room-temperature ferromagnetism enhancement in Ce_1−xCr_xO_2−δ nanoparticles (0.00≤x≤0.05), synthesized by a sol–gel-based method. Energy-dispersed X-ray spectrometry (EDS) analysis was used to estimate the dopant concentrations. The average crystallite sizes and particle size were estimated by X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. Both studies showed a gradual decrease in the size of the crystallites and particles for x>0.01. Cr can substitute for Ce in the crystal lattice, and the Raman measurements indicated that structural defects in the samples increased as a function of the Cr content in the CeO₂ crystal lattice. The surface topography, examined by scanning electron microscopy (SEM), showed that the undoped sample has a porous and loosely organized structure, whereas the Cr-doped samples exhibited a dense and compact structure. Magnetic measurements of the Ce_1−xCr_xO_2−δ samples at 27 ^oC showed a maximum remanent magnetization value of 0.01 emu/g for x=0.05. The nature and enhancement of room-temperature ferromagnetism was interpreted by taking into account the exchange interaction between Cr³⁺ ions and oxygen vacancies in CeO₂.     

Sol-gel growth of Gd2MoO6:Eu nanocrystalline layers on SiO2 spheres (SiO2@Gd2MoO6:Eu) and their luminescent properties

SiO₂@Gd₂MoO₆:Eu³⁺ core-shell phosphors were prepared by the sol-gel process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectra (EDS), transmission electron microscopy (TEM), photoluminescence (PL) spectra as well as kinetic decays were used to characterize the resulting SiO₂@Gd₂MoO₆:Eu³⁺ core-shell phosphors. The XRD results demonstrate that the Gd₂MoO₆:Eu³⁺ layers on the SiO₂ spheres begin to crystallize after annealing at 600 °C and the crystallinity increases with raising the annealing temperature. The obtained core-shell phosphors have a near perfect spherical shape with narrow size distribution (average size ca. 600 nm), are not agglomerated, and have a smooth surface. The thickness of the Gd₂MoO₆:Eu³⁺ shells on the SiO₂ cores could be easily tailored by varying the number of deposition cycles (50 nm for four deposition cycles). The Eu³⁺ shows a strong PL luminescence (dominated by ⁵D₀-⁷F₂ red emission at 613 nm) under the excitation of 307 nm UV light. The PL intensity of Eu³⁺ increases with increasing the annealing temperature and the number of coating cycles.     

Influence of laser power on the orientation and microstructure of CeO2 films deposited on Hastelloy C276 tapes by laser chemical vapor deposition

CeO₂ films were prepared on LaMnO₃/MgO/Gd₂Zr₂O₇ multi-coated Hastelloy C276 tapes by laser chemical vapor deposition at different laser power (P_L) from 46 to 101 W. Epitaxial (1 0 0) CeO₂ films were prepared at P_L = 46-93 W (deposition temperature, T_dep = 705-792 K). Epitaxial CeO₂ films had rectangular-shaped grains at P_L = 46-77 W (T_dep = 705-754 K), while square-shaped grains were obtained at P_L = 85-93 W (T_dep = 769-792 K). CeO₂ films showed a columnar microstructure. Epitaxial (1 0 0) CeO₂ films with rectangular grains exhibited full width at half maximum of ω-scan on (2 0 0) reflection and ?-scan on (2 2 0) reflection of 3.4-3.2° and 6.0-7.2°, respectively. The deposition rate of the epitaxial (1 0 0) CeO₂ films had a maximum of 4.6 μm h⁻¹ at P_L = 77 W (T_dep = 754 K).     

Facile fabrication of pomponlike microarchitectures of lanthanum molybdate via an ultrasound route

Pomponlike La₂(MoO₄)₃ microstructures assembled with single-crystalline nanoflakes have been facilely fabricated via a surfactant-assisted ultrasound route for the first time. Various synthesis conditions were examined, such as the surfactant concentration, the molecular structure of surfactants, and the pH value. The obtained pomponlike microstructures were characterized by X-ray diffraction (XRD), (field-emission) scanning electron microscopy [(FE)SEM], transmission electron microscopy (TEM), and nitrogen adsorption/desorption isotherms. It has been revealed that a minimum concentration of sodium dodecylsulfate (SDS) was required for the formation of pomponlike La₂(MoO₄)₃ microstructures. When the SDS concentration is above 0.02 mol L⁻¹, the pomponlike microstructures become more perfect, and the size is also increased with the increasing SDS concentration. Under the same sonication, similar pomponlike microstructures were obtained when a cationic surfactant, cetyltrimethyl ammonium bromide (CTAB), was used instead of the anionic surfactant SDS, indicating that the hydrophobic alkyl chains are an important factor for the formation of the pomponlike La₂(MoO₄)₃ microstructures. It is also found that the pomponlike La₂(MoO₄)₃ microstructures can only be obtained within an optimal pH range of 8.0–9.0 under sonication. Based on TEM, Fourier transform infrared spectroscopy (FT-IR) and solubilization experiment, a formation mechanism of pomponlike La₂(MoO₄)₃ microstructures was proposed, in which the collaborative action of surfactants and sonication plays a key role. Furthermore, the porosity of the pomponlike La₂(MoO₄)₃ microstructures were discussed.