Self propagating combustion synthesis and luminescent properties of nanocrystalline CeO2: Tb3+ (1-10 mol%) phosphors

Undoped and Tb3+ (1-10 mol%) doped CeO2 nanophosphors were synthesized by low temperature solution combustion method. The combustion derived products were well studied by Powder X-ray diffraction (PXRD), Scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR) and Ultraviolet visible (UV-Vis) characterizations. The thermoluminescence (TL) glow curves of CeO2: Tb3+ (1-10 mol%) nanophosphors exposed to c source (60Co) for various doses were discussed for the first time. Two TL glow peaks recorded at 182 and 262 degrees C respectively. The TL intensity at 262 degrees C peak increases linearly in the dose range 0.5-7 kGy. Further, this peak was well defined, intense and glow peak structure does not change with c-dose as a result, it was quite useful in TL dosimetry of ionizing radiations. The kinetic parameters associated with the glow peak were estimated using Chen's half width method. The photoluminescence emission (PLE) spectra consists of characteristic peaks at 544 and 655 nm which were attributed to D-5(4) -> F-7(5) and D-5(4) -> F-7(2) transitions of Tb3+ ions. The optimal concentration of Tb3+ ions was found to be 7 mol%. The color co-ordinates of CeO2: Tb3+ (1-10 mol%) located in green region. Hence, this phosphor was quite useful for display applications. (C) 2013 Elsevier B. V. All rights reserved.

Preparation and characterization of nanocrystalline CeO2 by precipitation method

CeO2 nanocrystalline particulates with different sizes were prepared by precipitation method using ethanol as dispersive and protective reagent. XRD spectra show that the synthesized CeO2 has cubic crystalline structure of space group O-H(5)-F-M3M, when calcination temperature is in the range of 250 similar to 800 degreesC. TEM images reveal that CeO2 particles are spherical in shape. The average size of the particles increases with the increase of calcination temperature. Thermogravimetric analysis indicates that the weight loss of precursor mainly depends on the calcination temperature, and little depends on the calcination time. Measurements of CeO2 relative density show that the relative density of CeO2 nanocrystalline powders increases with increasing CeO2 particle size.

Photovoltaic Properties and Quantum Size Effect in Nanocrystalline CeO2

Different size. nanocrystallines CeO2 were synthesized and their diffuse reflectance absorption spectra have heen measured. The absorption band in the region from 300 to 450 nm was assigned to the O2p-Ce2 4f transition. It was found that a strongly red-shifted broad continuum of the absorption band occured as the decrease of the partical size. We have also measured the surface photovoltage as function of wavelength by SPS technique. And the absorption band was resolved to two peaks with different photovoltaic properties. Photovoltaic quantum size effect was observed by FMSPS measurement.

Redox behavior of the model catalyst Pd/CeO2-x/Pt(111)

Photoelectron spectroscopy and scanning tunneling microscopy have been used to investigate how the oxidation state of Ce in CeO2-x(111) ultrathin films is influenced by the presence of Pd nanoparticles. Pd induces an increase in the concentration of Ce3+ cations, which is interpreted as charge transfer from Pd to CeO2-x(111) on the basis of DFT+U calculations. Charge transfer from Pd to Ce4+ is found to be energetically favorable even for individual Pd adatoms. These results have implications for our understanding of the redox behavior of ceria-based model catalyst systems.

Room temperature co-precipitation of nanocrystalline CeO2 and Ce0.8Gd0.2O1.9-delta powder

This paper describes a simple method to co-precipitate CeO2 and Ce0.8Gd0.2O1.9-delta with ammonium hydroxide from solvents such as: water, ethylene glycol, ethyl alcohol and isopropyl alcohol. Characterization by Raman spectroscopy and XRD evidenced the formation of a solid solution of gadolinium-doped ceria at room temperature. Nanometric particles with crystallite size of 3.1 nm were obtained during synthesis using ethyl alcohol as solvent. This is a promising result compared with those mentioned in the literature, in which the smallest crystallite size reported was, 6.5 nm. (c) 2006 Elsevier B.V. All rights reserved.

Fast densification and electrical conductivity of yttria-stabilized zirconia nanoceramics

Nanocrystalline 8YSZ (8 mol% yttria stabilized zirconia) bulk samples with grain sizes of 20-30 nm were synthesized by Sol-Gel method and then densified under a high pressure of 4.5 GPa at 1273 K for 10 min. The method led to the densification of 8YSZ to a relative density higher than 92% without grain growth. Fourier transmission Raman spectroscopy suggested that 8YSZ underwent a phase transition from the cubic phase to a phase mixture (tetragonal plus a trace of monoclinic) after the densification, which decreased the electrical conductivity to a certain degree as concluded from the impedance spectroscopy.

Influence of hydrogen peroxide in the preparation of nanocrystalline ceria

The influence of H2O2 in the preparation of nanocrystalline CeO2 has been investigated by treating solutions of Ce(III) with NaOH in the presence of different concentrations of H2O2. The resulting precipitated material was then examined by a range of techniques, including transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). A decrease in CeO2 crystallite size with increasing H2O2 concentration was observed. This was found to be associated with the formation of an amorphous material containing an η2-peroxide (O22-) species.

High quality CeO2 film grown on Si(111) substrate by using low energy dual ion beam deposition technology

By using the mass-analyzed low energy dual ion beam deposition technique, a high quality epitaxial, insulating cerium dioxide thin film with a thickness of about 2000 Angstrom, has been grown on a silicon (111) substrate. The component species, cerium and oxygen, are homogeneous in depth, and have the correct stoichiometry for CeO2. X-ray double-crystal diffraction shows that the full width at half maximum of the (222) and (111) peaks of the film are less than 23 and 32 s, respectively, confirming that the film is a perfect single crystal. (C) 1995 American Institute of Physics.

Oxygen vacancy formation in CeO2 and Ce1-xZrxO2 solid solutions:electron localization, electrostatic potential and structural relaxation

Ceria (CeO2) and ceria-based composite materials, especially Ce1-xZrxO2 solid solutions, possess a wide range of applications in many important catalytic processes, such as three-way catalysts, owing to their excellent oxygen storage capacity (OSC) through the oxygen vacancy formation and refilling. Much of this activity has focused on the understanding of the electronic and structural properties of defective CeO2 with and without doping, and comprehending the determining factor for oxygen vacancy formation and the rule to tune the formation energy by doping has constituted a central issue in material chemistry related to ceria. However, the calculation on electronic structures and the corresponding relaxation patterns in defective CeO2-x oxides remains at present a challenge in the DFT framework. A pragmatic approach based on density functional theory with the inclusion of on-site Coulomb correction, i.e. the so-called DFT + U technique, has been extensively applied in the majority of recent theoretical investigations. Firstly, we review briefly the latest electronic structure calculations of defective CeO2(111), focusing on the phenomenon of multiple configurations of the localized 4f electrons, as well as the discussions of its formation mechanism and the catalytic role in activating the O-2 molecule. Secondly, aiming at shedding light on the doping effect on tuning the oxygen vacancy formation in ceria-based solid solutions, we summarize the recent theoretical results of Ce1-xZrxO2 solid solutions in terms of the effect of dopant concentrations and crystal phases. A general model on O vacancy formation is also discussed; it consists of electrostatic and structural relaxation terms, and the vital role of the later is emphasized. Particularly, we discuss the crucial role of the localized structural relaxation patterns in determining the superb oxygen storage capacity in kappa-phase Ce1-xZr1-xO2. Thirdly, we briefly discuss some interesting findings for the oxygen vacancy formation in pure ceria nanoparticles (NPs) uncovered by DFT calculations and compare those with the bulk or extended surfaces of ceria as well as different particle sizes, emphasizing the role of the electrostatic field in determining the O vacancy formation.

Magnetic characteristics of nanocrystalline GaMnN films deposited by reactive sputtering

The magnetic characteristics of Ga1-xMnxN nanocrystalline films (x = 0.08 and x = 0.18), grown by reactive sputtering onto amorphous silica substrates (a-SiO2), are shown. Further than the dominant paramagnetic-like behaviour, both field- and temperature-dependent magnetization curves presented some particular features indicating the presence of secondary magnetic phases. A simple and qualitative analysis based on the Brillouin function assisted the interpretation of these secondary magnetic contributions, which were tentatively attributed to antiferromagnetic and ferromagnetic phases. © 2012 Elsevier Masson SAS. All rights reserved.

In-situ XANES experiments on Ni K-edge in mesoporous ZrO2-CeO2:Ni.

Ordered mesoporous ZrO2-CeO2 mixed oxides are potential candidates for catalytic applications. These systems, used as anodes in solid oxide fuel cells (SOFC), may lead to better performance of SOFCs, due to an enhancement on surface area, aiming to achieve a lower working temperature. The aim of this studies is to evaluate the reduction capacity of Ni2+ to Ni in ZrO2-x(mol)%CeO2 (x=50 and 90) samples impregnated with 60(wt.)%NiO. The synthesis was made with Zr and Ce chloride precursors, HCl aqueous solution, Pluronic P123, NH4OH to adjust the pH (3-4) and a teflon autoclave to perform a hydrothermal treatment (80oC/48h). The samples were dried and calcined, until 540oC in N2 and 4 hours in air. The NiO impregnation was made with an ethanol dispersion of Ni(NO3)£6H2O. The powder was calcinated in air until 350oC for 2 hours. Temperature-resolved XANES data at the Ni K-edge were collected at the DXAS beam line of the LNLS in transmission mode, using a Si(111) monochromator and a CCD detector. Sample preparation consisted of mixing »6mg of the powder samples with boron nitride and pressing into pellets. The data were acquired during an experiment of temperature programmed reduction (TPR) under a 5% H2/He until 600oC and mixtures of 20%CH4:5%O2/He, at temperatures from 400 to 600oC. All the reactions were monitored with a mass spectrometer. The data was analyzed with a linear combination fit of 2 standards for each valence number using Athena software. The Ni K-edge experiments demonstrated that for both contents of CeO2, NiO embedded in the porous zirconia-ceria matrix reduces at lower temperatures than pure NiO, revealing that the ZrO2-CeO2 support improves the reduction of impregnated NiO. Ni was oxidized to NiO after all reactions with methane and oxygen. Hydrogenated carbonaceous species were detected, but under reducing conditions, the hydrocarbon compounds are removed. The reaction of total oxidation of methane CH4:O2 (1:2 ratio) was observed at lower temperatures (around 400oC) for both samples.

Value added products from modified kaolins : new chemical routes to new markets

Chemical treatments of kaolins to produce nanocrystalline or "X-ray amorphous", stable aluminosilicates with variable - but reproducible - types of micro- and meso-porosity have been developed. These materials show cation exchange capacities and surface area values significantly higher (ranging from 10x to 100x) than kaolin and show good acid resistance to pH~3.0. The combination of these properties offers strong potential for many new applications of kaolin-derived materials in large worldwide markets such as environmental remediation and catalysis. Kaolin amorphous derivative (KAD) is well-suited to removal of many toxic metals down to ppb range from acid mine drainage. Engineering development trials of the KAD manufacturing process and the utilisation of KAD in polluted waters such as acid mine drainage indicates that scale-up from bench-scale is not a barrier to market entry.

溶胶-凝胶法合成二氧化铈纳米晶

用溶胶 -凝胶法合成了不同粒径的CeO2 纳米晶。XRD分析表明 ,不同焙烧温度下所合成的CeO2 纳米晶均属于立方晶系 ,空间群为O5H-FM3M。TEM分析表明 ,CeO2 纳米粒子呈球形 ,粒度分布集中 ,粒度随焙烧温度的增加而增大。X射线线宽法计算表明 ,CeO2纳米粒子越小 ,晶格畸变越大 ,晶粒发育越不完整 ,衍射强度越低。热失重分析表明 ,热失重率主要受焙烧温度的影响 ,焙烧时间的影响很小。红外光谱分析表明 ,纳米CeO2 比普通CeO2 具有更高的表面活性