Studies on Cu/CeO2: A new NO reduction catalyst

Fine particle and large surface area Cu/CeO2 catalysts of crystallite sizes in the range of 100-200 Angstrom synthesized by the solution combustion method have been investigated for NO reduction. Five percent Cu/CeO2 catalyst shows nearly 100% conversion of NO by NH3 below 300 degrees C, whereas pure ceria and Zr, Y, and Ca doped ceria show 85-95% NO conversion above 600 degrees C. Similarly NO reduction by CO has been observed over 5% Cu/CeO2 with nearly 100% conversion below 300 degrees C. Hydrocarbon (n-butane) oxidation by NO to CO2, N-2, and H2O has also been demonstrated over this catalyst below 350 degrees C making Cu/CeO2 a new NO reduction catalyst in the low temperature window of 150-350 degrees C. Kinetics of NO reduction over 5% Cu/CeO2 have also been investigated. The rate constants are in the range of 1.4 x 10(4) to 2.3 x 10(4) cm(3) g(-1) s(-1) between 170 and 300 degrees C. Cu/CeO2 catalysts are characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and electron paramagnetic resonance spectroscopy where Cu2+ ions are shown to be dispersed on the CeO2 surface. (C) 1999 Academic Press.

Combustion synthesis and properties of Ce1-xPrxO2-delta red ceramic pigments

Praseodymium-doped ceria red pigments, Ce1−xPrxO2−δ, x=0–0.5 have been prepared by the thermal decomposition of the redox compound Ce1−xPrx(N2H3COO)3·3H2O as well as by the combustion of aqueous solutions containing cerous nitrate, praseodymium nitrate and oxalyl dihydrazide (ODH)/ammonium acetate. Formation of the pigment has been confirmed by its characteristic red colour and reflectance spectra which shows the reflection edge not, vert, similar690 nm corresponding to charge transfer from the ligand orbitals to the localised 4f1 of Pr4+. The particulate properties of praseodymium-doped ceria pigments obtained from the combustion of redox compounds and redox mixtures are compared.

Monoclinic to cubic phase transformation in combustion synthesized gadolinium oxide

Gadolinium oxide, cerium oxide, and 10 mol% gadolinia doped ceria ceramic powders have been synthesized using combustion technique. Though the cubic gadolinia phase is stable at room temperature, single phase monoclinic gadolinia was obtained as a result of combustion synthesis using fuel lean and stoichiometric precursor compositions. This powder was subjected to calcination treatment and ceria doping to study the stability of phases and the rate of phase transformation from monoclinic to cubic gadolinia. It was found that monoclinic gadolinia transforms to cubic gadolinia upon calcination at temperatures less than 1200 degrees C. It was also found that rate of phase transformation is more for powder produced using fuel lean compositions; and the rate is enhanced upon ceria doping. (C) 2015 Elsevier Ltd. All rights reserved.

Stabilization of a complex perovskite superstructure under ambient conditions: Influence of cation composition and ordering, and evaluation as an SOFC cathode

Ba1.6Ca2.3Y1.1Fe5O13 is an Fe3+ oxide adopting a complex perovskite superstructure, which is an ordered intergrowth between the Ca2Fe2O5 and YBa2Fe3O8 structures featuring octahedral, square pyramidal, and tetrahedral B sites and three distinct A site environments. The distribution of A site cations was evaluated by combined neutron and X-ray powder diffraction. Consistent with the Fe3+ charge state, the material is an antiferromagnetic insulator with a Néel temperature of 480-485 °C and has a relatively low d.c. conductivity of 2.06 S cm-1 at 700 °C. The observed area specific resistance in symmetrical cell cathodes with the samarium-doped ceria electrolyte is 0.87 Ω cm2 at 700 °C, consistent with the square pyramidal Fe3+ layer favoring oxide ion formation and mobility in the oxygen reduction reaction. Density functional theory calculations reveal factors favoring the observed cation ordering and its influence on the electronic structure, in particular the frontier occupied and unoccupied electronic states. © 2010 American Chemical Society.

Preparation and Electrical Properties of New Oxide Ion Conductors Ce6-xGdxMoO15-delta (0.0 <= x <= 1.8)

A series of oxide ion conductors Ce6-xGdxMoO15-delta (0.0 <= x <= 1.8) have been prepared by the sol-gel method. Their properties were characterized by differential thermal analysis/thermogravimetry (DTA/TG), X-ray diffraction (XRD), Raman, IR, X-ray photoelectron spectroscopy (XPS), and AC impedance spectroscopy. The XRD patterns showed that the materials were single phase with a cubic fluorite structure. The conductivity of Ce6-xGdxMoO15-delta increases as x increases and reaches the maximum at x = 0.15. The conductivity of Ce4.5Gd1.5MoO15-delta is sigma(t) = 3.6 x 10(-3) S/cm at 700 degrees C, which is higher than that of Ce4.5/6Gd1.5/6O2-delta (sigma(t) = 2.6 x 10(-3) S/cm), and the corresponding activation energy of Ce4.5Gd1.5MoO15-delta (0.92 eV) is lower than that of Ce4.5/6Gd1.5/6O2-delta (1.18 eV).

Nitrate-citrate combustion synthesis and properties of Ce1-xSmxO2-x/2 solid solutions

A nitrate-citrate combustion route to synthesize nanocrystalline samarium-doped ceria powders for solid electrolyte ceramics is presented. This route is based on the gelling of nitrate solutions by the addition of citric acid and ammonium hydroxide, followed by an intense combustion process due to an exothermic redox reaction between nitrate and citrate ions. The influence of ignition temperature on the characteristics of the powders was studied. The change of the crystal structure with the content of doped Sm was investigated. High temperature X-ray, and Raman scattering were used to characterize the sample. The lattice constant and unit volume increase with doping level and increasing temperature. Dense ceramic samples prepared by uniaxial pressing and sintering in air were also studied.

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.

Materiais à base de óxidos com estrutura do tipo perovskite e compósitos como ânodos de PCES

This work was focused on the analysis of transport, thermomechanical and electrochemical properties of a series of perovskite-like oxide materials and composites for potential applications as anodes of intermediate-temperature solid oxide fuel cells (SOFCs) with lanthanum gallate and silicate solid electrolytes. The primary attention was centered on A(Mn,Nb)O3-δ (A = Sr, Ca) and (La,Sr)(Mn,Ti)O3-based systems, lanthanum chromite substituted with acceptor-type and variable-valence cations, and various Ni-containing cermets. Emphasis was given to phase stability of the materials, their crystal structure, microstructure of porous electrode layers and dense ceramics, electronic conductivity, Seebeck coefficient, oxygen permeability, thermal and chemical induced expansion, and anodic overpotentials of the electrodes deposited onto (La,Sr)(Ga,Mg)O3- and La10(Si,Al)6O27- based electrolyte membranes. In selected cases, roles of oxygen diffusivity, states of the transition metal cations relevant for the electronic transport, catalytically active additives and doped ceria protective interlayers introduced in the model electrochemical cells were assessed. The correlations between transport properties of the electrode materials and electrochemical behavior of porous electrodes showed that the principal factors governing anode performance include, in particular, electronic conduction of the anode compositions and cation interdiffusion between the electrodes and solid electrolytes. The latter is critically important for the silicatebased electrolyte membranes, leading to substantially worse anode properties compared to the electrochemical cells with lanthanum gallate solid electrolyte. The results made it possible to select several anode compositions exhibiting lower area-specific electrode resistivity compared to known analogues, such as (La,Sr)(Cr,Mn)O3-δ.

Improvement in the Reduction Behavior of Novel ZrO(2)-CeO(2) Solid Solutions with a Tubular Nanostructure by Incorporation of Pd

In this work, 1 wt % Pd/ZrO(2)-CeO(2) mixed oxide nanotubes with 90 mol % CeO(2) were synthesized following a very simple, high-yield procedure and their properties were characterized by synchrotron radiation X-ray diffraction, X-ray absorption near-edge spectroscopy (XANES), and scanning and high-resolution transmission electron microscopy (SEM and HRTEM). In situ XANES experiments were carried out under reducing conditions to investigate the reduction behavior of these novel nanotube materials. The Pd/CeO(2)-based nanotubes exhibited the cubic phase (Fm3m space group). The nanotube walls were composed of nanoparticles with an average crystallite size of about 7 nm, and the nanotubes exhibited a large specific surface area (85 m(2).g(-1)). SEM and HRTEM studies showed that individual nanotubes were composed of a curved sheet of these nanoparticles. Elemental analysis showed that the Ce:Zr:Pd ratios appeared to be approximately constant across space, suggesting compositional homogeneity in the samples. XANES results indicated that the extent of reduction of these materials is low and that the Ce(4+) state is in the majority over the reduced Ce(3+) state. The results suggest that Pd cations-most likely Pd(2+)-form a Pd-Ce-Zr oxide solid solution and that the Pd(2+) is stabilized against reduction in this phase. However, incorporation of the Pd (1 wt %) into the crystal lattice of the nanotubes also appeared to destabilize Ce(4+) against reduction to Ce(3+) and caused a significant increase in its reducibility.

Síntese e caracterização de NiO-CGO para anodo e eletrólitos sólidos e base de Céria para SOFC

The direct use of natural gas makes the Solid Oxide Fuel Cell (SOFC) potentially more competitive with the current energy conversions technologies. The Intermediate Temperature SOFC (IT-SOFC) offer several advantages over the High Temperature SOFC (HT-SOFC), which includes better thermal compatibility among components, fast start with lower energy consumption, manufacture and operation cost reduction. The CeO2 based materials are alternatives to the Yttria Stabilized Zirconia (YSZ) to application in SOFC, as they have higher ionic conductivity and less ohmic losses comparing to YSZ, and they can operate at lower temperatures (500-800°C). Ceria has been doped with a variety of cations, although, the Gd3+ has the ionic radius closest to the ideal one to form solid solution. These electrolytes based in ceria require special electrodes with a higher performance and chemical and termomechanical compatibility. In this work compounds of gadolinia-doped ceria, Ce1-xGdxO2-δ (x = 0,1; 0,2 and 0,3), used as electrolytes, were synthesized by polymeric precursors method, Pechini, as well as the composite material NiO - Ce0,9Gd0,1O1,95, used as anode, also attained by oxide mixture method, mixturing the powders of the both phases calcinated already. The materials were characterized by X ray diffraction, dilatometry and scanning electronic microscopy. The refinement of the diffraction data indicated that all the Ce1-xGdxO2-δ powders were crystallized in a unique cubic phase with fluorite structure, and the composite synthesized by Pechini method produced smaller crystallite size in comparison with the same material attained by oxide mixture method. All the produced powders had nanometric characteristics. The composite produced by Pechini method has microstructural characteristics that can increase the triple phase boundaries (TPB) in the anode, improving the cell efficiency, as well as reducing the mass transport mechanism effect that provokes anode degradation

Influência do método de síntese e caracterização de pós compósitos de NiO- Ce1-xEuxO2-δ para anodos catalíticos de células a combustível

Fuel cells are electrochemical devices that convert chemical energy into electricity. Due to the development of new materials, fuel cells are emerging as generating clean energy generator. Among the types of fuel cells, categorized according to the electrode type, the solid oxide fuel cells (SOFC) stand out due to be the only device entirely made of solid particles. Beyond that, their operation temperature is relatively high (between 500 and 1000 °C), allowing them to operate with high efficiency. Another aspect that promotes the use of SOFC over other cells is their ability to operate with different fuels. The CeO2 based materials doped with rare earth (TR+3) may be used as alternatives to traditional NiO-YSZ anodes as they have higher ionic conductivity and smaller ohmic losses compared to YSZ, and can operate at lower temperatures (500-800°C). In the composition of the anode, the concentration of NiO, acting as a catalyst in YSZ provides high electrical conductivity and high electrochemical activity of reactions, providing internal reform in the cell. In this work compounds of NiO - Ce1-xEuxO2-δ (x = 0.1, 0.2 and 0.3) were synthesized from polymeric precursor, Pechini, method of combustion and also by microwave-assisted hydrothermal method. The materials were characterized by the techniques of TG, TPR, XRD and FEG-SEM. The refinement of data obtained by X-ray diffraction showed that all powders of NiO - Cex-1EuxO2-δ crystallized in a cubic phase with fluorite structure, and also the presence of Ni. Through the characterizations can be proved that all routes of preparation used were effective for producing ceramics with characteristics suitable for application as SOFC anodes, but the microwave-assisted hydrothermal method showed a significant reduction in the average grain size and improved control of the compositions of the phases

Efeito da Gália como aditivo de sinterização em eletrólitos cerâmicos à base de céria sintetizados pelo método de complexação de cátions

Fuel cells are considered one of the most promising ways of converting electrical energy due to its high yield and by using hydrogen (as fuel) which is considered one of the most important source of clean energy for the future. Rare earths doped ceria has been widely investigated as an alternative material for the electrolyte of solid oxide fuel cells (SOFCs) due to its high ionic conductivity at low operating temperatures compared with the traditional electrolytes based on stabilized zirconia. This work investigates the effect of gallium oxide (Gallia) as a sintering aid in Eu doped ceria ceramic electrolytes since this effect has already been investigated for Gd, Sm and Y doped ceria electrolytes. The desired goal with the use of a sintering aid is to reduce the sintering temperature aiming to produce dense ceramics. In this study we investigated the effects on densification, microstructure and ionic conduction caused by different molar fraction of the dopants europium (10, 15 and 20%) and gallium oxide (0.3, 0.6 and 0.9%) in samples sintered at 1300, 1350 and 1450 0 C. Samaria (10 and 20%) doped ceria samples sintered between 1350 and 1450 °C were used as reference. Samples were synthesized using the cation complexation method. The ceramics powders were characterized by XRF, XRD and SEM, while the sintered samples were investigated by its relative density, SEM and impedance spectroscopy. It was showed that gallia contents up to 0.6% act as excellent sintering aids in Eu doped ceria. Above this aid content, gallia addition does not promote significant increase in density of the ceramics. In Ga free samples the larger densification were accomplished with Eu 15% molar, effect expressed in the microstructure with higher grain growth although reduced and surrounded by many open pores. Relative densities greater than 95 % were obtained by sintering between 1300 and 1350 °C against the usual range 1500 - 1600 0 C. Samples containing 10% of Sm and 0.9% of Ga reached 96% of theoretical density by sintering at 1350 0 C for 3h, a gain compared to 97% achieved with 20% of Sm and 1% of Ga co-doped cerias sintered at 1450 0 C for 24 h as described in the literature. It is found that the addition of gallia in the Eu doped ceria has a positive effect on the grain conductivity and a negative one in the grain boundary conductivity resulting in a small decrease in the total conductivity which will not compromise its application as sintering aids in ceria based electrolytes. Typical total conductivity values at 600 and 700 °C, around 10 and 30 mS.cm -1 respectively were reached in this study. Samples with 15% of Eu and 0.9 % of Ga sintered at 1300 and 1350 °C showed relative densities greater than 96% and total conductivity (measured at 700 °C) between 20 and 33 mS.cm -1 . The simultaneous sintering of the electrolyte with the anode is one of the goals of research in materials for SOFCs. The results obtained in this study suggest that dense Eu and Ga co-doped ceria electrolytes with good ionic conductivity can be sintered simultaneously with the anode at temperatures below 1350 °C, the usual temperature for firing porous anode materials

Síntese citrato-hidrotermal e caracterização eletroquímica de LSCF para aplicação como catodo em célula a combustível de temperatura intermediária

The lanthanum strontium cobalt iron oxide (La1-xSrxCo1-yFeyO3 LSCF) is the most commonly used material for application as cathode in Solid Oxide Fuel Cells (SOFCs), mainly due to their high mixed ionic electronic conductivity between 600 and 800ºC. In this study, LSCF powders with different compositions were synthesized via a combination between citrate and hydrothermal methods. As-prepared powders were calcined from 700 to 900°C and then characterized by X-ray fluorescence, X-ray diffraction, thermal analyses, particle size analyses, nitrogen adsorption (BET) and scanning electronic microscopy. Films of composition La0,6Sr0,4Co0,2Fe0,8O3 (LSCF6428), powders calcined at 900°C, were screen-printed on gadolinium doped ceria (CGO) substrates and sintered between 1150 and 1200°C. The effects of level of sintering on the microstructure and electrochemical performance of electrodes were evaluated by scanning electronic microscopy and impedance spectroscopy. Area specific resistance (ASR) exhibited strong relation with the microstructure of the electrodes. The best electrochemical performance (0.18 ohm.cm2 at 800°C) was obtained for the cathode sintered at 1200°C for 2 h. The electrochemical activity can be further improved through surface activation by impregnation with PrOx, in this case the electrode area specific resistance decreases to values as low as 0.12 ohm.cm2 (800°C), 0.17 ohm.cm2 (750°C) and 0.31 ohm.cm2 (700°C). The results indicate that the citrate-hydrothermal method is suitable for the attainment of LSCF particulates with potential application as cathode component in intermediate temperature solid oxide fuel cells (IT-SOFCs)

Deposição de filmes de ZrO2 modificados sobre substratos metálicos

This work makes use of the Pechini process for synthesis of the solutions and the dip-coating process for the addition of zirconium oxide films pure and doped cerium metal substrates. The metals with ceramic substrates were subjected to severe conditions of salinity. The x-ray fluorescence of the substrate showed a great diversity of chemical elements. The x-ray diffraction of the samples showed the phase of iron substrate because the thickness of nano-thin film. Tests using an LPR probe showed that the film presents with zirconia corrosion independent of film thickness. The substrates of ZrO2-doped ceria showed low chemical attack of the salt in films with less than 15 dives. The results imply that ultrathin films are shown in protecting metallic substrates

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.