Fabrication of cerium oxide nanoparticles: Characterization and optical properties

Ceria (CeO2) is a technologically important rare earth material because of its unique properties and various engineering and biological applications. A facile and rapid method has been developed to prepare ceria nanoparticles using microwave with the average size 7 nm in the presence of a set of ionic liquids based on the bis (trifluoromethylsulfonyl) imide anion and different cations of 1-alkyl-3-methyl-imidazolium. The structural features and optical properties of the nanoparticles were determined in depth with X-ray powder diffraction, transmission electron microscope, N-2 adsorption-desorption technique, dynamic light scattering (DLS) analysis, FTIR spectroscopy, Raman spectroscopy, UV-vis absorption spectroscopy, and Diffuse reflectance spectroscopy. The energy band gap measurements of nanoparticles of ceria have been carried out by UV-visible absorption spectroscopy and diffuse reflectance spectroscopy. The surface charge properties of colloidal ceria dispersions in ethylene glycol have been also studied. To the best of our knowledge, this is the first report on using this type of ionic liquids in ceria nanoparticle synthesis. (C) 2011 Elsevier Inc. All rights reserved.

Preferential CO oxidation over a copper-cerium oxide catalyst in a microchannel reactor

The activity of a 5-wt% Cu/CeO2-x catalyst during preferential CO oxidation in hydrogen-rich gas mixtures was studied in a microchannel reactor. The CO concentration dropped from 1 vol.% to 10 ppm at a selectivity of 60%, at a temperature of 190 degrees C, and a weight hour space velocity (WHSV) of 55,000 cm(3) g(-1) h(-1). Both the CO concentration and the temperature increased when the WHSV was increased from 50,000 to 500,000 cm(3) g(-1) h(-1). An increase of the O-2 concentration from a 1.2 to 3 fold excess reduced the CO concentration to 10 ppm in a broad temperature interval of 50 degrees C at WHSVs up to 275,000 cm(3) g(-1) h(-1). The preferential CO oxidation could be carried out at higher flow rates and at higher selectivities in the microchannel reactor compared to a fixed-bed flow reactor. (C) 2008 Elsevier B.V. All rights reserved.

Experimental design and batch experiments for optimization of Cr(VI) removal from aqueous solutions by hydrous cerium oxide nanoparticles

Hydrous cerium oxide (HCO) was synthesized by intercalation of solutions of cerium(III) nitrate and sodium hydroxide and evaluated as an adsorbent for the removal of hexavalent chromium from aqueous solutions. Simple batch experiments and a 2⁵ factorial experimental design were employed to screen the variables affecting Cr(VI) removal efficiency. The effects of the process variables; solution pH, initial Cr(VI) concentration, temperature, adsorbent dose and ionic strength were examined. Using the experimental results, a linear mathematical model representing the influence of the different variables and their interactions was obtained. Analysis of variance (ANOVA) demonstrated that Cr(VI) adsorption significantly increases with decreased solution pH, initial concentration and amount of adsorbent used (dose), but slightly decreased with an increase in temperature and ionic strength. The optimization study indicates 99% as the maximum removal at pH 2, 20 °C, 1.923 mM of metal concentration and a sorbent dose of 4 g/dm³. At these optimal conditions, Langmuir, Freundlich and Redlich–Peterson isotherm models were obtained. The maximum adsorption capacity of Cr(VI) adsorbed by HCO was 0.828 mmol/g, calculated by the Langmuir isotherm model. Desorption of chromium indicated that the HCO adsorbent can be regenerated using NaOH solution 0.1 M (up to 85%). The adsorption interactions between the surface sites of HCO and the Cr(VI) ions were found to be a combined effect of both anion exchange and surface complexation with the formation of an inner-sphere complex.

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.

Titania and tungsten doped titania thin films on glass; active photocatalysts

Acidification of an isopropanol solution containing mixtures of [Ti(OPri)(4)] and [W(OEt)(5)] produced solutions from which various TiO2, WO3 and TiO2/WO3 thin films could be obtained by dip coating and annealing. The films were analysed by X-ray diffraction, SEM/EDAX, Raman, electronic spectra, contact angle and photoactivity with respect to destruction of an over layer of stearic acid. The TiO2/WO3 films were shown to be mixtures of two phases TiO2 and WO3 rather than a solid solution TixWyO2. The 2% tungsten oxide doped titania films were shown to be the most effective photocatalysts. All of the TiO2 and TiO2/WO3 films showed light induced superhydrophillicity. (C) 2002 Elsevier Science Ltd. All rights reserved.

Sub-nA spatially resolved conductivity profiling of surface and interface defects in ceria films

Spatial variability of conductivity in ceria is explored using scanning probe microscopy (SPM) with galvanostatic control. Ionically blocking electrodes are used to probe the conductivity under opposite polarities to reveal possible differences in the defect structure across a thin film of CeO2. Data suggests the existence of a large spatial inhomogeneity that could give rise to constant phase elements during standard electrochemical characterization, potentially affecting the overall conductivity of films on the macroscale. The approach discussed here can also be utilized for other mixed ionic electronic conductor (MIEC) systems including memristors and electroresistors, as well as physical systems such as ferroelectric tunneling barriers.

Understanding the Flash Sintering of Rare-Earth-Doped Ceria for Solid Oxide Fuel Cell

A novel electrical current applied technique known as flash sintering has been applied to rapidly (within 10 min) densify electrolytes including Ce_0.8Gd_0.2O_1.9 (GDC20), Ce_0.9Gd_0.1O_1.95 (GDC10), and Ce_0.8Sm_0.2O_1.9 (SDC20) for application in Solid Oxide Fuel Cells (SOFCs). The densification temperature for the three electrolytes was 554°C, 635°C, and 667°C, respectively, which is far below conventional sintering temperatures. All specimens after flash sintering maintained the pure fluorite structure and exhibited a well-densified microstructure. To investigate the flash-sintering mechanism, we have applied Joule heating effect with blackbody radiation theory, and found that this theory could reasonably interpret the flash-sintering phenomenon by matching theoretically calculated temperature with the real temperature. More importantly, one of the materials inherent properties, the electronic conductivity, has been found correlated with the onset of flash sintering, which indicates that the electrons and holes are the primary current carriers during the start of flash-sintering process. As a result, potential densification mechanisms have been discussed in terms of spark plasma discharge.

Comparative analysis of the DC performance of DG MOSFETs on highly-doped and near-intrinsic silicon layers

A comparison of dc characteristics of fully depleted double-gate (DG) MOSFETs with respect to low-power circuit applications and device scaling has been performed by two-dimensional device simulation. Three different DG MOSFET structures including a conventional N+ polysilicon gate device with highly doped Si layer, an asymmetrical P+/N+ polysilicon gate device with low doped Si layer and a midgap metal gate device with low doped Si layer have been analysed. It was found that DG MOSFET with mid-gap metal, gates yields the best dc parameters for given off-state drain leakage current and highest immunity to the variation of technology parameters (gate length, gate oxide thickness and Si layer thickness). It is also found that an asymmetrical P+/N+ polysilicon gate DG MOSFET design offers comparable dc characteristics, but better parameter immunity to technology tolerances than a conventional DG MOSFET. (C) 2004 Elsevier Ltd. All rights reserved.

Lanthanide-doped luminescent ionogels

Ionogels are solid oxide host networks con. ning at a meso-scale ionic liquids, and retaining their liquid nature. Ionogels were obtained by dissolving lanthanide(III) complexes in the ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide, [C(6)mim][Tf2N], followed by confinement of the lanthanide-doped ionic liquid mixtures in the pores of a nano-porous silica network. [C(6)mim][Ln(tta)(4)], where tta is 2-thenoyltrifluoroacetonate and Ln = Nd, Sm, Eu, Ho, Er, Yb, and [choline](3)[Tb(dpa)(3)], where dpa = pyridine-2,6-dicarboxylate (dipicolinate), were chosen as the lanthanide complexes. The ionogels are luminescent, ion-conductive inorganic-organic hybrid materials. Depending on the lanthanide(III) ion, emission in the visible or the near-infrared regions of the electromagnetic spectrum was observed. The work presented herein highlights that the confinement did not disturb the first coordination sphere of the lanthanide ions and also showed the excellent luminescence performance of the lanthanide tetrakis beta-diketonate complexes. The crystal structures of the complexes [C(6)mim][Yb(tta)(4)] and [choline](3)[Tb(dpa)(3)] are reported.

Near infrared electroluminescence from neodymium complex-doped polymer light emitting diodes

Organic light emitting diode devices employing organometallic Nd(9-hydroxyphenalen-1-one)(3) complexes as near infrared emissive dopants dispersed within poly(N-vinylcarbazole) (PVK) host matrices have been fabricated by spin-casting layers of the doped polymer onto glass/indium tin oxide (ITO)/3,4-polyethylene-dioxythiophene-polystyrene sulfonate (PEDOT) substrates. Room temperature electroluminescence, centered at similar to 1065 nm. was observed from devices top contacted by evaporated aluminum or calcium metal cathodes and was assigned to transitions between the F-4(3/2) -> I-4(11/2) levels of the Nd3+ ions. In particular, a near infrared irradiance of 8.5 nW/mm(2) and an external quantum efficiency of 0.007% was achieved using glass/ITO/PEDOT/PVK:Nd(9-hydroxyphenalen-1-one)(3)/Ca/Al devices. (c) 2005 Elsevier B.V. All rights reserved.

Narrow bandwidth red electroluminescence from solution-processed lanthanide-doped polymer thin films

Narrow bandwidth red electroluminescence from OLED devices fabricated using a simple solution-based approach is demonstrated. A spin-casting method is employed to fabricate organic light emitting diode (OLED) devices comprising a poly(N-vinylcarbazole) (PVK) host matrix doped with a europium beta-diketonate complex, Eu(dbM)(3)(Phen) (dibenzoylmethanate, dbm; 1,10-phenanthroline, Phen) on glass/ indium tin oxide (ITO)/3,4-polyethylene-dioxythiophene-polystyrene sulfonate (PEDOT) substrates. Saturated red europium ion emission, based on the (5)Do ->F-7(2) transition, is centered at a wavelength of 612 nm with a full width at half maximum of 3.5 rim. A maximum external quantum efficiency of 6.3 x 10(-2) cd/A (3.1 X 10(-2)%) and a maximum luminance of 130 cd/M-2 at 400 mA/cm(2) and 25 V is measured for ITO/PEDOT/PVK:Eu(dbM)3(Phen)/Ca/Al devices. This measured output luminance is comparable to that of devices fabricated using more sophisticated small molecule evaporation techniques. (c) 2005 Elsevier B.V All rights reserved.

Growth of SrS thin films by pulsed-laser deposition

High-quality luminescent thin films of strontium sulphide (SrS) with excellent stoichiometry have been grown by pulsed-laser deposition. The crystallinity, stoichiometry and cathodoluminescence (CL) have been investigated for the films deposited onto two differently coated glass substrates. Furthermore the importance of post-deposition annealing has been studied. SrS thin films grown at 450 degrees C onto glass substrates coated with tin-doped indium oxide show good crystallinity, with a preferred orientation along the (200) axis. Cerium-doped SrS (SrS:Ce) gives a strong blue CL output at 400 nm. Energy-dispersive X-ray spectroscopy shows that the films are stoichiometric and that the stoichiometry is controllable by varying deposition parameters.

Solution-based synthesis of cobalt-doped ZnO thin films

Undoped and cobalt-doped (1-4 wt.%) ZnO polycrystalline, thin films have been fabricated on quartz substrates using sequential spin-casting and annealing of simple salt solutions. X-ray diffraction (XRD) reveals a wurzite ZnO crystalline structure with high-resolution transmission electron microscopy showing lattice planes of separation 0.26 nm, characteristic of (002) planes. The Co appears to be tetrahedrally co-ordinated in the lattice on the Zn sites (XRD) and has a charge of + 2 in a high-spin electronic state (X-ray photoelectron spectroscopy). Co-doping does not alter the wurzite structure and there is no evidence of the precipitation of cobalt oxide phases within the limits of detection of Raman and XRD analysis. Lattice defects and chemisorbed oxygen are probed using photoluminescence and Raman spectroscopy - crucially, however, this transparent semiconductor material retains a bandgap in the ultraviolet (3.30-3.48 eV) and high transparency (throughout the visible spectral regime) across the doping range. © 2012 Elsevier B.V.

Atmospheric pressure chemical vapour deposition of boron doped titanium dioxide for photocatalytic water reduction and oxidation

Boron-doped titanium dioxide (B-TiO) films were deposited by atmospheric pressure chemical vapour deposition of titanium(iv) chloride, ethyl acetate and tri-isopropyl borate on steel and fluorine-doped-tin oxide substrates at 500, 550 and 600 °C, respectively. The films were characterised using powder X-ray diffraction (PXRD), which showed anatase phase TiO at lower deposition temperatures (500 and 550 °C) and rutile at higher deposition temperatures (600 °C). X-ray photoelectron spectroscopy (XPS) showed a dopant level of 0.9 at% B in an O-substitutional position. The ability of the films to reduce water was tested in a sacrificial system using 365 nm UV light with an irradiance of 2 mW cm. Hydrogen production rates of B-TiO at 24 μL cm h far exceeded undoped TiO at 2.6 μL cm h. The B-TiO samples were also shown to be active for water oxidation in a sacrificial solution. Photocurrent density tests also revealed that B-doped samples performed better, with an earlier onset of photocurrent. © 2013 The Owner Societies.

Co-tape casting fabrication, field assistant sintering and evaluation of a coke resistant La0.2Sr0.7TiO3-Ni/YSZ functional gradient anode supported solid oxide fuel cell

The ability to directly utilize hydrocarbons and other renewable liquid fuels is one of the most important issues affecting the large scale deployment of solid oxide fuel cells (SOFCs). Herein we designed La_0.2Sr_0.7TiO₃-Ni/YSZ functional gradient anode (FGA) supported SOFCs, prepared with a co-tape casting method and sintered using the field assisted sintering technique (FAST). Through SEM observations, it was confirmed that the FGA structure was achieved and well maintained after the FAST process. Distortion and delamination which usually results after conventional sintering was successfully avoided. The La_0.2Sr_0.7TiO₃-Ni/YSZ FGA supported SOFCs showed a maximum power density of 600mWcm^-2 at 750°C, and was stable for 70h in CH₄. No carbon deposition was detected using Raman spectroscopy. These results confirm the potential coke resistance of La_0.2Sr_0.7TiO₃-Ni/YSZ FGA supported SOFCs.