Structural and textural studies of NiO impregnation in mesoporous ZrO2-CeO2 for\ud catalysis applications.

The synthesis of zirconia-based ordered mesoporous structures for catalytic applications is a\ud research area under development. These systems are also potential candidates as anodes in\ud intermediate temperature solid oxide fuel cells (it-SOFC) due to an enhancement on their surface area\ud [1-4]. The structural features of mesoporous zirconia-ceria materials in combination with oxygen\ud storage/release capacity (OSC) are crucial for various catalytic reactions. The direct use of\ud hydrocarbons as fuel for the SOFC (instead of pure H2), without the necessity of reforming and\ud purification reactors can improve global efficiency of these systems [4].\ud The X-ray diffraction data showed that ZrO2-x%CeO2 samples with x>50 are formed by a larger\ud fraction of the cubic phase (spatial group Fm3m), while for x<50 the major crystalline structure is the\ud tetragonal phase (spatial group P42/nmc). The crystallite size of the cubic phase increases with\ud increase in ceria content. The tetragonal crystallite size decreases when ceria content increases. After\ud impregnation, the Rietveld analysis showed a NiO content around 60wt.% for all samples. The lattice\ud parameters for the ZrO2 tetragonal phase are lower for higher ZrO2 contents, while for all samples the\ud cubic NiO and CeO2 parameters do not present changes. The calculated densities are higher for higher\ud ceria content, as expected. The crystallite size of NiO are similar (~20nm) for all samples and 55nm\ud for the NiO standard.\ud Nitrogen adsorption experiments revealed a broader particle size distribution for higher CeO2\ud content. The superficial area values were around 35m2/g for all samples, the average pore diameter and\ud pore volumes were higher when increasing ceria content. After NiO impregnation the particle size\ud distribution was the same for all samples, with two pore sizes, the first around 3nm and a broader peak\ud around 10nm. The superficial area increased to approximately 45m2/g for all samples, and the pore\ud volume was also higher after impregnation and increased when ceria content increased.\ud These results point up that the impregnation of NiO improves the textural characteristics of the\ud pristine material. The complementary TEM/EDS images present a homogeneous coating of NiO\ud particles over the ZrO2-x%CeO2 support, showing that these samples are excellent for catalysis\ud applications.\ud [1] D. Y. Zhao, J. Feng, Q. Huo, N. Melosh, G. H. Fredrickson, B. F. Chmelka, G. D. Stucky, Science\ud 279, 548-552 (1998).\ud [2] C. Yu, Y. Yu, D. Zhao, Chem. Comm. 575-576 (2000).\ud [3] A. Trovarelli, M. Boaro, E. Rocchini, C. de Leitenburg, G. Dolcetti, J. Alloys Compd. 323-324\ud (2001) 584-591.\ud [4] S. Larrondo, M. A. Vidal, B. Irigoyen, A. F. Craievich, D. G. Lamas, I. O. Fábregas, et al. Catal.\ud Today 107–108 (2005) 53-59.CNPqFAPES

Structural and reduction studies of ZrO2-CeO2:Ni for application in SOFC anodes.

Zirconia-ceria solid-solutions are extensively used as promoters for three-way catalysts, which are applied in the control of NOx, CO and hydrocarbons emission from automotive exhausts. In addition, thesematerials can be used as anodes in solid oxide fuel cells (SOFCs) operated with hydrocarbons. There areonly few works on ZrO2-CeO2 ordered mesoporous materials for catalytic applications and for anodes inSOFCs. The interest in these anodes relies on the fact that ZrO2-CeO2materials are mixed ionic/electronic conductors in reducing atmosphere and, therefore, fuel oxidation is produced on its entire surface, while it only occurs in the [anode/electrolyte/gas] interface (triple-phase boundaries) for electronic conductors.\ud In this work, a synthesis method was developed usingZr and Ce chloride precursors, HCl aqueous solution, Pluronic P123 as the structure directing agent, NH4OH to adjust the pH (3-4) and a Teflon autoclave to perform hydrothermal treatment (80ºC/48 hours). The samples were dried and calcined, until 540ºC in N2and 4 hours in air. The X-ray diffraction data showed that powders with higher CeO2 content are formed by a larger fraction of the cubic CeO2 phase, while for a lower CeO2content the major crystalline structure is the tetragonal ZrO2 phase. The NiO impregnation was made with an ethanol dispersion of Ni(NO3)×6H2O. The resulting powder was calcinated in air until 350ºC for 2 hours. Temperature-programmed reduction (TPR) data were collected in order to evaluate the reduction profiles of ZrO2-x%CeO2:Ni samples in H2/Ar atmosphere. Results showed lower reduction temperatures for all ceria content in samples comparing to a NiO standard

Zirconia-Ceria Porous Systems

Neste trabalho foram desenvolvidas sínteses de ZrO2-x%CeO2, baseadas na preparação da sílica mesoporosa ordenada SBA-15, utilizando um molde de co-polímero tribloco Pluronic P-123, diversos precursores de zircônio e cério e diferentes métodos. Os métodos de síntese testados foram com: precursores a base de cloreto hidratado (com x=50, 70 e 90), precursores a base de cloreto anidro (x=50 e 90), precursores a base de nitrato (x=90), solução supersaturada de nitrato (x=90), do tipo híbrido com Zr, Ce e Si (com 10%mol de Si e x=90), paliçada de Si (com 10 e 30%mol de Si e x=90) e paliçada de Si com temperatura de síntese de 40°C (com 30%mol de Si e x=90). Visando obter paredes compostas por fase cristalina única e grande área supercial, para futuras aplicações em catálise. Os compósitos polímero/(zircônio-cério) sintetizados a partir de cloretos formam uma estrutura lamelar organizada, que se transforma num sistema poroso desordenado após a calcinação para a retirada do molde. O processo de decomposição/remoção do molde até 540°C produz mudanças de fase nos precursores a base dos metais utilizados, além das transformações morfológicas. Para uma concentração de 90% de CeO2 obtém-se um material poroso com paredes homogêneas de estrutura fcc e de maior estabilidade mecânica. Os valores de área supercial e volume de poros dependem fundamentalmente do método de preparação do material e independem da concentração de CeO2. Aumentos signicativos da área supercial (~100m²/g) e do volume de poros (~0,4cm³/g) são obtidos a partir da introdução de sílica nesses sistemas. Foram alcançados área supercial aproximadamente 6 vezes maior e tamanho de cristalito ~4 vezes superior à do material similar nanocristalino preparado por gel-combustão. Esses valores também são iguais aos reportados para os melhores materiais porosos a base de zircônia-céria, preparados por outros métodos, encontrados na literatura.In this work synthesis of ZrO2-x%CeO2 were developed, based on the formation of ordered mesoporous silica SBA-15, using the triblock co-polymer Pluronic P-123 as template, different precursors of zirconium and cerium and dierent methods. The tested synthesis methods were with: hydrated chloride precursors (with x=50, 70 and 90), anhydrous chloride precursors (x=50 and 90), nitrate precursors (x=90), supersaturated nitrate solution (x=90), hybrid type with Zr, Ce and Si (with 10%mol of Si and x=90), Si palisade (with 10 and 30%mol of Si, and x=90) and Si palisade with synthesis temperature of 40°C (with 30%mol of Si and x=90). Aiming to obtain crystalline single phase walls and large supercial area, for future applications in catalysis. The composites polymer/zirconium-cerium synthesized from chloride precursors formed an organized lamellar structure, which transforms into a disordered porous system after the calcination to remove the template. The template decomposition/removal up to 540°C produces phase transformations in the metallic precursors, besides morphological changes. A CeO2 content of 90% resulted in a porous material with homogeneous walls of fcc structure and better mechanical stability. The values of supercial area and pore volume depend mostly on the preparation method rather than the CeO2 concentration. Signicant increases on supercial area (~100m²/g) and pore volume (~0.4cm³/g) were obtained with the introduction of silica into the material. Supercial area ~6 times larger and crystallite size ~4 times superior to a nanocrystalline similar material, made by gel-combustion were attained. These figures are also equal to the ones reported for the best porous zirconia-ceria materials, prepared by other routes, found in the literature

Syntesis and Characterization of ZrO2-CeO2/Ni nanocatalysts for application in solid oxide fuel cell anodes

Compósitos mesoporosos de ZrO2-CeO2 estão sendo desenvolvidos devido às suas excelentes propriedades morfológicas e estruturais, necessárias para várias aplicações, que incluem sensores de gás, catálise automotiva e ânodos de células a combustível de óxido sólido. Nesse trabalho foi desenvolvido um novo método de síntese sol-gel com template cooperativo utilizando o polímero tribloco P-123 e os cloretos de Zr/Ce como precursores dos óxidos. Foram sintetizados ZrO2-x(mol)%CeO2 com x = 50, 70 e 90% de CeO2, uma vez que esses materiais apresentam melhores características para aplicações catalíticas. Dois processos de calcinação diferentes foram testados (até 540 e 400ºC). O NiO (60% m/m) foi impregnado para que o material obtenha a condutividade eletrônica necessária para aplicação em ânodos de SOFC. Os resultados de difração de raios X indicaram sistemas cuja fase cristalográfica predominante é a cúbica tipo fluorita (a fase tetragonal é minoritária). Fase única cúbica foi obtida para 90% de CeO2 após a calcinação até 400ºC. Dentre as características morfológicas dos materiais calcinados até 540ºC, os resultados de adsorção/dessorção de N2, imagens de microscopia eletrônica e espalhamento de raios X a baixos ângulos apresentaram aglomerados cristalinos de ZrO2-CeO2, formando um sistema mesoporoso bicontínuo, aleatéorio e sem forma definida, homogêneo em composição, com área superficial intermediária (30-40 m2/g), com alta dispersividade de poros/partículas. A calcinação a 400ºC apresentou menor dispersividade, menor tamanho de poros e maior área superficial (> 100 m2/g). O recobrimento da matriz de ZrO2-CeO2 pelas nanopartículas de NiO é superficial, sem obstrução ou preenchimento dos poros. A partir da redução à temperatura programada, observou-se que independentemente do conteúdo de CeO2, a porcentagem de redução do Ce4+ foi maior e ocorreu a menores temperaturas (início da redução em 300ºC) do que o padrão de CeO2 (750ºC). Esse comportamento se repete com as amostras após a incorporação com NiO, que se reduz a Ni também em baixas temperaturas (320ºC). A atividade catalítica para conversão do CH4 em oxidação total foi similar para ambas temperaturas de calcinação, para 90% de CeO2, atingindo 50% de conversão de CH4 para ~ 540ºC. Nos experimentos de absorção de raios X in-situ, na borda K do Ni e na borda LIII do Ce, foi possível observar que todos os conteúdos de CeO2 são ativos para oxidação parcial e total de CH4, assim como decomposição do CH4 e oxidação do CO, que ocorreu em torno de 600ºC. Os resultados de espectroscopia de impedância eletroquímica mostraram que, materiais com alto conteúdo de CeO2, apresentam baixa resistividade, de 0,97 cm2 a 750ºC em atmosfera de 5% CH4/3\\%H2O/N2. Portanto, o material desenvolvido neste trabalho apresenta as melhores propriedades morfológicas, estruturais, elétricas e catalíticas relatadas na literatura para aplicações como ânodo de SOFC e catalisador, comparado a materiais similares relatados na literatura.Mesoporous ZrO2-CeO2 composites are being developed due to their excellent morphological and structural properties, which are necessary for their use in several applications, including gas sensors, three way catalysts (TWC) and solid oxide fuel cells (SOFCs). In this work a new synthesis method was developed based on a template cooperative sol-gel approach, using the tri-block polymer P-123 and Zr/Ce chlorides as the oxides\' precursors. Since high cerium oxide quantities lead to better catalytic performance, the ZrO2-x(mol)%CeO2 were synthesized with x = 50, 70 and 90. Two different calcination processes were tested (until 540 and 400 ºC). NiO was impregnated in order to obtain enough electronic conductivity for their application as SOFC anodes. X-ray diffraction results showed that these systems are biphasic and crystallized preferentially into cubic fluorite type structure together with smaller quantities of the tetragonal zirconia-ceria phase. A 100% cubic phase was retained for 90% of CeO2 after 400 ºC calcination. Textural and morphological characteristics for 540ºC calcination evaluated from N2 sorption, electronic microscopy images and small angle X-ray scattering revealed a two-density (pores/particles) random crystalline clusters of mesoporous ZrO2-CeO2, with homogeneous composition, average superficial area (30-40 m2/g), high dispersivity of pores/particle sizes. Calcination until 400 ºC presented a narrower pore size distribution and smaller pores, with higher superficial area (> 100 m2/g). It was observed that NiO particles formed an uniform layer over the ZrO2-CeO2 without filling or blocking the zirconia-ceria pores. Temperature programmed reduction experiments showed that for all ceria contents the reduction percentage of Ce4+ species in the samples was higher and at lower temperatures (beginning of reduction at 300 ºC) than standard CeO2 (750 ºC). After NiO impregnation this behavior was similar, with NiO reducing at lower temperatures (320 ºC) as well. Catalytic activity for methane total oxidation reaction was similar for both calcination temperatures, for 90% CeO2, showing 50% of CH4 conversion around 540 ºC. Absorption X-ray in-situ experiments at Ni K-edge and Ce LIII-edge showed that all ceria contents are active for total and partial methane oxidation, CH4 decomposition and CO oxidation at 600 ºC. Electrochemical impedance spectroscopy measurements showed low resistivity for higher ceria content, 0,97 Ocm2 at 750 ºC in 5% CH4/3% H2O/N2 atmosphere. Resuming, the material developed in this work presents the best morphological, structural, electrical and catalytical properties for applications as SOFC anode and catalyst, compared to similar materials reported in the literature

A Novel Synthesis Route of Mesoporous gamma Alumina from Polyoxohydroxide Aluminum

Mesoporous gamma-aluminas (gamma-Al2O3) were synthesized starting from an unusual precursor of polyoxohydroxide aluminum (POHA). This precursor was obtained from aluminum oxidation in alkaline water-ethanol solvent in the presence of d-glucose that induces the formation of a gel, which leads to the POAH powder after ethanolic treatment Precipitated POHAs were calcined at different temperatures (300, 400, 700 and 900 degrees C) resultmg m the metastable gamma-Al(2)0(3) phase. Whereas at 300 degrees C no gamma-Al(2)0(3) phase was formed, unexpectedly, mesoporous gamma-Al(2)0(3) was obtained at 400 degrees C having a high specific surface area (282 m(2)/g) and a narrow pore size distribution At higher temperatures, the aluminas had the expected decrease in surface area 166 m(2)/g (700 degrees C) and 129 m(2)/g (900 degrees C), respectively The structural change from POHA to alumina calcined at 400 degrees C occurs directly without the need to isolate the hydroxide or oxyhydroxide aluminum precursors Both POHA and transition aluminas were characterized by Fourier Transform Infrared spectroscopy (FTIR), X-ray diffraction (XRD), N-2 sorption and Scanning Electron Microscopy (SEM) These findings show an alternative route to produce high standard aluminas.Fundacao de Apoio a Pesquisa do Estado de Sao Paulo - FAPESPCAPESCNPqUniv Sao Paulo, Dept Engn Quim DEQ, Escola Engn Lorena, Estr Municipal Campinho S-N, BR-12602810 Lorena, SP, BrazilUniv Fed Sao Paulo UNIFESP, Dept Ciencias Exatas & Terra, Rua Sao Nicolau 210, BR-09913030 Diadema, SP, BrazilUniv Fed ABC, Ctr Engn Modelagem & Ciencias Sociais Aplicadas, Santo Andre, SP, BrazilUniv Sao Paulo, Inst Quim, Ave Prof Lineu Prestes 748, BR-05508900 Sao Paulo, SP, BrazilUniv Sao Paulo, Escola Engn Lorena, Polo Ind, Dept Engn Mat DEMAR, Gleba Al-6 S-N, BR-12602810 Lorena, SP, BrazilUniv Fed Sao Paulo UNIFESP, Dept Ciencias Exatas & Terra, Rua Sao Nicolau 210, BR-09913030 Diadema, SP, BrazilFAPESP: 2015/06064-6, 2013/08166-5, 2016/05496-2Web of Scienc

Effects of synthesis conditions on the nanostructre of CexZr1-xO2 mesoporous ceramics.

CexZr1-xO2 (0.5 ≤ x ≤ 0.9) were synthesized with Zr and Ce chloride precursors, using the triblock\ud copolymer Pluronic P123 and HCl (2 mol/L). The pH adjustment was performed in two ways: synthesis\ud A used 11.4 mL of a NH4OH solution added at once to the initial mixture, composed by metal precursors\ud and template in HCl; synthesis B was done by dripping slowly until the change of pH value (between 3\ud and 6). In this work, CexZr1-xO2 samples synthesized by these two processes are compared. The effects of\ud pH values in materials characteristics were also evaluated. These samples were analysed by X-Ray\ud Diffraction (XRD) with Rietveld refinement, and Nitrogen Adsorption/Desorption. In both processes, the\ud studied materials presented two crystalline phases of CexZr1-xO2 solid solution: cubic and tetragonal. The\ud synthesis A also presented a tetragonal phase of ZrO2. The average crystallite size and the Brunauer-\ud Emmett-Teller (BET) surface area are bigger in process A. Both processes give samples with a\ud mesoporous structure.FAPES

A Novel Synthesis Route of Mesoporous γ-Alumina from Polyoxohydroxide Aluminum

<div><p>Mesoporous gamma-aluminas (γ-Al2O3) were synthesized starting from an unusual precursor of polyoxohydroxide aluminum (POHA). This precursor was obtained from aluminum oxidation in alkaline water-ethanol solvent in the presence of d-glucose that induces the formation of a gel, which leads to the POAH powder after ethanolic treatment. Precipitated POHAs were calcined at different temperatures (300, 400, 700 and 900 °C) resulting in the metastable γ-Al2O3 phase. Whereas at 300 °C no γ-Al2O3 phase was formed, unexpectedly, mesoporous γ-Al2O3 was obtained at 400 ºC having a high specific surface area (282 m2/g) and a narrow pore size distribution. At higher temperatures, the aluminas had the expected decrease in surface area: 166 m2/g (700 °C) and 129 m2/g (900 °C), respectively. The structural change from POHA to alumina calcined at 400 ºC occurs directly without the need to isolate the hydroxide or oxyhydroxide aluminum precursors. Both POHA and transition aluminas were characterized by Fourier Transform Infrared spectroscopy (FTIR), X-ray diffraction (XRD), N2 sorption and Scanning Electron Microscopy (SEM). These findings show an alternative route to produce high standard aluminas.</p></div