Fotocatalisadores baseados em nanopartículas de dióxido de titânio modificados fornecem soluções em potencial para a mineralização de poluentes orgânicos em meio aquoso. Agentes modificadores têm sido amplamente investigados com o objetivo de promover a fotoativação pela luz visível. Foram estudadas a nível fundamental até aqui, as modificações estruturais, texturais e óticas causadas pela introdução de silício e nitrogênio na rede da titânia. Titânias puras (TiO2) e modificadas nanoestruturadas, particularmente titânias modificadas com silício (TiO2-SiO2), com razões atômicas Si/Ti de 0,1, 0,2 e 0,3 foram sintetizadas pelo método sol-gel a partir da hidrólise ácida de isopropóxido de titânio(IV) e tetraetoxisilano. As metodolo-gias sintéticas desenvolvidas tentaram aderir aos princípios da Química Verde, dispensando o uso de atmosfera inerte e temperatura e pressão elevadas, o que foi alcançado utilizando-se, principalmente, a agitação ultrassônica. Titânias modificadas com silício e dopadas com ni-trogênio (TiO2-SiO2-N) foram obtidas a partir do pré-tratamento de TiO2-SiO2 a 500 °C ao ar e então submetidas ao fluxo de amônia (NH3) a 600 °C por 1-3 h e, após resfriamento, foram recozidas a 400 °C ao ar. Amostras distintas foram caracterizadas, na forma de pó seco e após calcinação entre 400 600 °C, por difração de raios X, adsorção de nitrogênio, microscopia eletrônica de varredura e espectroscopia de refletância difusa no UV-Visível. As titânias pu-ras, obtidas principalmente variando-se a razão de hidrólise, foram cristalizadas na forma de anatásio como fase predominante até 600 °C, além de traços de brookita presente até 500 °C. O rutilo foi identificado a partir de 600 °C como fase minoritária, embora apresentando tama-nhos de cristal significativamente maiores que os estimados para o cristal de anatásio. As titâ-nias modificadas com até 20% de silício apresentaram notável estabilidade térmica, evidenci-ada pela presença exclusiva de anatásio até 900 °C. Foi também observado o aparecimento de macroporos com diâmetro médio em torno de 55 nm após calcinação a 400 °C, diferentemente do que se observou nas amostras em geral. A introdução de baixo teor de silício assegurou às titânias calcinadas valores elevados de área específica, atribuído ao efeito de contenção acentuada na taxa de crescimento do cristal. As titânias modificadas com silício e as titânias puras obtidas com taxa de hidrólise 25:1 para a razão H2O : Ti apresentaram mesoporos com diâmetros médios de mesma dimensão do cristal. As titânias modificadas com silício e dopa-das com nitrogênio apresentaram absorção na região visível entre 400-480 nm, com discreta redução da energia de band gap para as transições eletrônicas consideradas. Titânias calcina-das a 300−400 °C apresentaram desempenho fotocatalítico semelhante ao TiO2 P25 da De-gussa sob irradiação UV, na degradação do azo corante Reactive Yellow 145 em soluções a-quosas em pH 5 a 20 ±1°C

Nanopartículas de dióxido de titânio vêm sendo extensamente empregadas como fotocatalisa-dores, já que são eficientes na degradação de diversos poluentes. Visando a obtenção de titâ-nias com diferentes propriedades, realizaram-se sínteses através do método sol-gel, a partir da hidrólise do tetraisopropóxido de titânio (IV) TIPP e seguindo-se os princípios da Química Verde, dispensando-se temperaturas e pressões elevadas. Foi estudada a influência de dife-rentes parâmetros, como: pH, solvente, razão molar álcool/TIPP e ordem de adição dos rea-gentes. Foram obtidas titânias na forma cristalina anatásio, nanométricas, com elevadas áreas superficiais específicas e predominantemente mesoporosas. Visando-se obter titânias com melhores propriedades óticas, isto é, capazes de sofrer a fotoativação pela luz visível, foram sintetizadas titânias dopadas e co-dopadas com os metais ferro e rutênio (Fe3+ e Ru3+) e o a-metal N (N3 ). A síntese desses materiais também foi realizada através do método sol-gel, sendo a dopagem realizada durante o processo de hidrólise. As amostras foram caracterizadas na forma de pó por difração de raios-X, adsorção-dessorção de nitrogênio, microscopia ele-trônica de varredura e espectroscopia de refletância difusa no UV-Visível. A titânia pura a-presentou como única fase cristalina o anatásio, quando calcinada até 400 °C, com a presença de traços de brookita. A partir de 600 °C, observou-se o aparecimento da fase rutilo, que em 900°C foi a única fase encontrada na titânia. A dopagem com Ru3+dificultou a transformação de fase anatásio para rutilo, ao contrário da dopagem com Fe3+. O processo de co-dopagem acelerou a formação de rutilo, que se apresentou como única fase nas amostras calcinadas a 600 ºC. As titânias dopadas apresentaram uma leve diminuição na energia de bandgap, sendo os dopantes capazes de deslocar a absorção para o vermelho. Foram realizados testes fotoca-talíticos visando à degradação do azocorante Reactive Yellow 145 com lâmpada de vapor de mercúrio de 125 W a fim de se comparar as atividades fotocatalíticas das titânias puras, dopa-das e co-dopadas, calcinadas a 300°C. De todas as titânias sintetizadas, a titânia pura foi a que melhor degradou o corante, tendo um desempenho semelhante ao do TiO2 P25, da Evo-nik

This work deals on the preparation of silicon oxycarbide (SiOC) and silicon boron oxycarbide (SiBOC) ceramics from pyrolysis involving alkoxysilanes with different organic groups. Boron content, organic substituent and annealing time were evaluated on crystallization and composition of resulting ceramics. B-free precursors composed of methyltriethoxysilane (MTES), phenyltriethoxysilane (PTES) and vinyltrimethoxysilane (VTMS) were obtained by the sol-gel method, whilst B-containing precursors were prepared by adding to each alkoxysilane a proper amount of boric acid resulting in B/Si atomic ratios of 0.1 and 0.5. Precursors were pyrolyzed at 1500 ºC for 1 and 3 h to produce respective SiOC and SiBOC ceramics. X-ray diffraction (XRD) patterns revealed enhanced SiC phase crystallization for PTES-derived ceramics, followed by those containing vinyl and methyl groups, which was also confirmed by X-ray photoelectron spectroscopy (XPS) from percentages of SiºC and Si?O bonds. Csp2 and Csp3 amounts varied among ceramics, indicating direct influence of organic substituent on conductive carbon phase development. Boron addition induced the growth of SiC crystallites, having more evident effect in matrices with higher proportions of amorphous fraction and lower residual carbon amounts. Organic group nature, boron content and annealing time played an important role for production and evolution of SiC and C phases into ceramics.

This article reports the characterization of mesoporous Nb2O5 synthesized by the sol-gel method for application in photocatalysis. The emerging contaminant methylviologen was employed for photocatalytic tests. Parameters inherent to the synthesis process, such as stirring rate, aging temperature, and calcination temperature, were employed for a range of values to improve the synthetic route. The powders obtained were characterized by thermogravimetric analysis, X-ray diffraction, scanning and transmission electron microscopy, specific surface area, infrared spectroscopy, energy-dispersive spectroscopy, and diffuse reflectance spectroscopy. In samples calcined at 450 °C, a mixture of amorphous and hexagonal phases was observed, with a predominance of the former, while in samples calcined at 650 °C the orthorhombic phase predominated. Samples calcined at 450 °C exhibited larger specific surface areas. Mesoporous structures were confirmed for samples T8035M450 and T8045mi450, which displayed higher photoactivity, with roughly 90% removal of methylviologen.

This article reports the synthesis and characterization of pure and N-, B-, and Ag-doped TiO2 and the ability of these oxides to photodegrade methylene blue (MB) under sunlight or UV-ABC radiation. The compounds were synthesized using the sol-gel method and characterized by scanning electron microscopy, X-ray diffraction, diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy. Photocatalytic efficiency was significantly increased by N-doping, resulting in 98% MB decomposition under UV-ABC irradiation for 180 min. Ag- and B-doped TiO2 lowered MB degradation rates to 52 and 73%, respectively, compared with pure TiO2. The same behavior was observed with exposure to UV-Vis, with 88, 65, 60, and 42% MB removal with N-doped, pure, B-doped, and Ag-doped TiO2, respectively. Under visible light alone, N-doped TiO2 exhibited higher photocatalytic efficiency than commercial P25-type TiO2. Photocatalysis with N-doped TiO2 proved to be a promising alternative for MB degradation, given the potential of employing solar energy, thus minimizing operating costs.

Lithium cobalt oxide, LiCoO2, widely used as cathode in lithium ion batteries was synthesized and their structural and electronic properties investigated. The crystalline powders were prepared by the sol-gel method with four complexing agents: citric acid, glycine, starch and gelatin. These syntheses were compared with the blank test (without complexing agent). The X-ray diffraction and vibrational spectroscopy allowed the identification of the rhombohedral phase LiCoO2 (R3m) as the only or principal crystalline component in all samples. A small fraction of a second phase of cubic spinel Co3O4 was observed in the samples of starch, gelatin and the blank test. The Rietveld refinements showed small structural variations, indicating reduced influence of the complexing agents on the synthesis. The theoretical HOMO-LUMO (highest occupied molecular orbital-lowest unoccupied molecular orbital) gap values are in agreement to those estimated by diffuse reflectance spectroscopy (DRS). The scanning electron microscopy (SEM) showed morphological pattern regardless of the complexing agent used, showing an alternative method.

Crystalline ZnO nanorods with wurtzite-like structure and average diameter of 90 nm and length >1 µm, was prepared by calcination (700 ºC) of a Zn(II)/albumen hybrid obtained by sol-gel method, by the reaction of Zn(II) acetate and egg white (albumen), in aqueous solution. The material was characterized by powder X-ray diffraction (XRD), scanning electron (SEM) and transmission electron microscopy (TEM), thermogravimetric analysis (TGA/DTA), N2 adsorption/desorption (BET method), FT-IR and photoluminescence (PL) spectroscopy. The surface area was determined to be 6.91 m² g-1 by BET method. The TGA/DTA thermal events were consistent with the decomposition of albumen at 300 ºC and final formation of ZnO at 578.5 ºC. The results showed that albumen act as template playing essential role on defining the formation of ZnO nanorods with brush-like morphology.

SiO2/CeO2 mixed oxide (designated as SC) with variable ceria contents, SC1 = 5.6, SC2 = 8.0 and SC3 = 13.0 wt%, prepared by the sol-gel processing method, were obtained as amorphous solids possessing specific surface areas of SC1 = 463, SC2 = 474 and SC3 = 460 m²g-1. Phosphate ions were immobilized onto the surface of these solids through Ce-O-P bonding by immersing SC into a phosphoric acid solution. Solids with the following P contents were obtained (in atom %): SCP1 = 0.60, SCP2 = 0.71 and SCP3 = 1.63. The binding energy peak P 2p3/2 at ca. 134.0 eV, observed by XPS, and the 31P MAS NMR single peak, observed at ca. -10 ppm, revealed that H2PO4- is the species present on the surface of the matrices. Using pyridine as a molecular probe, only Brønsted acid sites could be detected. The amount of these acid sites, determined by ammonia gas adsorption on the surface, reached the following values for each phosphate-treated solid: SCP1 = 0.37, SCP2 = 0.43 and SCP3 = 0.51 mmol g-1.

SiO2-TiO2 materials prepared by sol-gel method were evaluated in the photocatalytic degradation of diuron. The materials were prepared with and without surfactant cetyltrimethylammonium chloride at different temperatures (25, 50 and 100 ºC). The samples were characterized by N2 adsorption-desorption measurements, scanning electron microscopy, X-ray diffraction, ultraviolet-visible diffuse reflectance spectroscopy and infrared diffuse reflectance spectroscopy. The results showed that the materials synthesized with the surfactant had higher surface areas and band-gap values similar to anatase. All materials were more active than the commercial catalyst P-25 and better performance was achieved using the surfactant in the material synthesis.

This paper describes the synthesis and characterization of organic/inorganic hybrid materials formed from TiO2 nanoparticles and polyaniline (PANI). The preparation method is based on a sol-gel technique using titanium tetra-isopropoxide as oxide precursor, and two synthetic routes to the hybrids formation were employed, based on the addition of aniline after or before the sol formation. Different amounts of aniline were used to verify this effect on the characteristics of the formed materials. Samples were characterized by electronic spectroscopy, Raman spectroscopy, Fourier transformed infrared spectroscopy, thermal analysis, X-ray diffractometry and cyclic voltammetry. Results show that the different experimental routes are successful to produce hybrids formed by oxides nanoparticles and polyaniline in its conducting form, the emeraldine salt. There are no strong differences between the samples obtained by the two synthetic routes employed, except by the amount of polymer in the final material.