Síntese e caracterização textural do catalisador CeO2/TiO2 obtido via sol-gel: fotocatálise do composto modelo hidrogenoftalato de potássio

Este trabalho descreve um método de modificação do TiO2 obtido pelo processo sol-gel, através da adição de óxido de cério no momento da síntese. O material foi caracterizado por adsorção de N2 a 77K. A adição de CeO2 aumenta a área específica do catalisador em 135% e reduz o diâmetro de poros. A atividade catalítica desses materiais foi verificada frente à reação de foto-decomposição do hidrogenoftalato de potássio e comparada ao TiO2 comercial P25 da Degussa.

On the difficulties of present theoretical models to predict the oxidation state of atomic Au adsorbed on regular sites of CeO2(111)

The electronic structure and oxidation state of atomic Au adsorbed on a perfect CeO2(111) surface have been investigated in detail by means of periodic density functional theory-based calculations, using the LDA+U and GGA+U potentials for a broad range of U values, complemented with calculations employing the HSE06 hybrid functional. In addition, the effects of the lattice parameter a0 and of the starting point for the geometry optimization have also been analyzed. From the present results we suggest that the oxidation state of single Au atoms on CeO2(111) predicted by LDA+U, GGA+U, and HSE06 density functional calculations is not conclusive and that the final picture strongly depends on the method chosen and on the construction of the surface model. In some cases we have been able to locate two well-defined states which are close in energy but with very different electronic structure and local geometries, one with Au fully oxidized and one with neutral Au. The energy difference between the two states is typically within the limits of the accuracy of the present exchange-correlation potentials, and therefore, a clear lowest-energy state cannot be identified. These results suggest the possibility of a dynamic distribution of Au0 and Au+ atomic species at the regular sites of the CeO2(111) surface.

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.

Oxidação de propeno em catalisadores de CuO suportados em CeO2/y-alumina/cordierita

No presente trabalho, procedeu-se a preparação e caracterização de catalisadores ambientais à base de óxido de cobre suportado em -alumina (suporte)/cordierita (substrato) e que tinham como promotor o óxido de cério. A argila foi conformada via eletroforese na forma de monolitos. Após queima à 1100°C, estes foram triturados, selecionado-se partículas com diâmetro entre 0,297 < Dp < 0,590 mm. Para a obtenção de -alumina e óxidos de cério e cobre sobre as partículas, utilizou-se a técnica de impregnação a seco (umidade incipiente), usando soluções de Al(OH)3, Ce(NO)3.6H2O e Cu(NO)3.3H2O, respectivamente . Após cada impregnação, os catalisadores foram secos e calcinados. A caracterização dos catalisadores foi feita através de experimentos de TPR (Redução à Temperatura Programada), microscopia eletrônica de varredura e espectrofotometria de absorção atômica, tendo como reação teste a oxidação de propeno com excesso de oxigênio. A caracterização da argila precursora da cordierita foi realizada através da difratometria de raios X . Procurou-se determinar neste trabalho os tipos de sítios de óxido de cobre (através do ensaio de TPR) e valores de ordens de reação e energia de ativação para a reação de oxidação de propeno através de estudos de cinética aplicada, relacionando-se os resultados com valores da literatura. Os valores de energia de ativação obtidos neste trabalho, para a oxidação de propeno, variaram de 82 kJ/mol à 100 kJ/mol e as ordens parciais de reação do propeno de 0,73 à 1,11. Todos os resultados acima foram obtidos em reator diferencial . O efeito da adição de óxido de cério nestes catalisadores também foi abordado neste trabalho.

Activity and characterization by XPS, HR-TEM, Raman spectroscopy, and BET surface area of CuO/CeO2-TiO2 catalysts

Structural and textural studies of a CuO/TiO2 System modified by cerium oxide were conducted using Raman spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and N-2 absorption (BET specific surface area). The introduction of a minor amount of CeO2 (Ce0.09Ti0.82O1.91CU0.09 sample) resulted in a material with the maximum surface area value. The results of Raman spectroscopy revealed the presence of only two crystalline phases, TiO2 anatase and CeO2 cerianite, with well-dispersed copper species. TEM micrographs showed a trend toward smaller TiO2 crystallites when the cerium oxide content was increased. The XPS analysis indicated the rise of a second peak in Ti 2p spectra with the increasing amount of CeO2 located at higher binding energies than that due to the Till in a tetragonal symmetry. The CuO/TiO2 system modified by CeO2 displayed a superior performance for methanol dehydrogenation than the copper catalyst supported only on TiO2 or CeO2.

X-ray photoelectron spectroscopy, x-ray absorption spectroscopy, and x-ray diffraction characterization of CuO-TiO2-CeO2 catalyst system

X-ray photoelectron spectroscopy (XPS), x-ray diffraction (XRD), and x-ray absorption spectroscopy (XAS) techniques have been applied to characterize the surface composition and structure of a series of CuO-TiO2-CeO2 catalysts. For a small loading of cerium, ceria was mainly dispersed on the titania surface and a minor amount of CeO2 crystallite appeared. At higher loading of cerium, the CeO2 phase increased and the atomic Ce/Ti ratio values were smaller than the nominal composition, as a consequence of cerium agglomeration. This result suggests that only a fraction of cerium can be spread on the titania surface. For titanium-based mixed oxide, we observed that cerium is found as Ce3+ uniquely on the surface. The atomic Cu/(Ce+Ti) ratio values showed no influence from cerium concentration on the dispersion of copper, although the copper on the surface was shown to be dependent on the cerium species. For samples with a high amount of cerium, XPS analysis indicated the raise of second titanium species due cerium with spin-orbit components at higher binding energies than those presented by Ti4+ in a tetragonal structure. The structural results obtained by XAS are consistent with those obtained by XRD and XPS. (C) 2001 American Vacuum Society.

Síntese e caracterização textural do catalisador CeO2/TiO2 obtido via sol-gel: fotocatálise do composto modelo hidrogenoftalato de potássio

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Influence of the substitution of Y2O3 for CeO2 on the mechanical and microstructural properties of silicon nitride

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Si3N4 ceramic cutting tool sintered with CeO2 and Al2O3 additives with AlCrN coating

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Synthesis and sintering of ZrO2-CeO2 powder by use of polymeric precursor based on Pechini process

Nanocrystalline ZrO2-12 mol % CeO2 powders were synthesized using a polymeric precursor method based on the Pechini process. X-ray diffraction (XRD) patterns showed that the method was effective to synthesize tetragonal zirconia single-phase. The mean crystallite size attained ranges from 6 to 15 nm. The BET surface areas were relatively high reaching 97 m(2)/g. Studies by nitrogen adsorption/desorption on powders, dilatometry of the compacts, and transmission electron microscopy (TEM) of the powders, were also developed to verify the particles agglomeration state. Both citric acid : ethylene glycol ratio and calcination temperature affected the powder morphology, which influenced the sinterability and microstructure of the sintered material, as showed by scanning electron microscopy (SEM). (C) 2001 Kluwer Academic Publishers.

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.

Influence of La2O3, Pr2O3 and CeO2 on the nonlinear properties of SnO2 multicomponent varistors

The influence of La2O3, Pr2O3 and CeO2 on a new class of polycrystalline ceramics with nonlinear properties based on SnO2, was investigated. La2O3 and Pr2O3 were found to precipitate at the grain boundary region, causing a considerable increase in the nonlinear behavior. It was found that CeO2 forms a solid solution in the bulk but. unlike La2O3 and Pr2O3, it does not increase the nonlinear behavior. A higher nonlinear coefficient of similar to80 was obtained for La2O3-doped SnO2-based systems. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Characterization of an all sol-gel electrochromic device WO3/Ormolyte/CeO2-TiO2

Electrochemical lithium intercalation in thin films of CeO2-TiO2 and WO3, prepared by the sol-gel technique was investigated with cyclic voltammetry and spectroelectrochemical techniques in propylene carbonate solutions. A solid state system having the configuration WO3/Ormolyte/CeO2-TiO2 has been assembled. The solid electrolyte, an organically modified electrolyte (ormolyte), was prepared with different [O]/[Li] ratios. The transmittance variation of this system during a potentiostatic step from -0.7 V to 0.8 V was about 35% at 550 nm.

CeO2 nanoparticles synthesized by a microwave-assisted hydrothermal method: evolution from nanospheres to nanorods

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Preparation of CeO2 by a simple microwave-hydrothermal method

Cerium carbonate hydroxide (orthorhombic Ce(OH)CO3) hexagonal-shaped microplates were synthesized by a simple and fast microwave-hydrothermal method at 150 degrees C for 30 min. Cerium nitrate, urea and cetyltrimethylammonium bromide were used as precursors. Ceria (cubic CeO2) rhombus-shape was obtained by a thermal decomposition oxidation process at 500 degrees C for 1 h using as- synthesized Ce(OH)CO3. The products were characterized by X-ray powder diffraction, field-emission scanning electron microscopy, thermogravimetric analysis and Fourier transformed infrared spectroscopy. The use of microwave-hydrothermal method allowed to obtain cerium compounds at low temperature and shorter time compared to other synthesis methods. (C) 2008 Elsevier B.V. All rights reserved.