Síntese e caracterização de TiO2 puro e modificado para aplicações ambientais

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 400600 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 1C

Sínteses e caracterizações de TiO2 puro, dopado e co-dopado pelo método sol-gel e suas atividades fotocatalíticas

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 900C 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 C. 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 300C. 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

A vertically aligned carbon nanotube/fiber based electrode for economic hydrogen production by water electrolysis

Electrolysis is the most mature form of hydrogen production. Unfortunately, water electrolysis has not yet achieved the efficiency and the cost levels required for any practical application. In order to enhance the current density, modification of the electrolyte and the electrode morphology are the most popular approaches. Recently there have been numerous reports on how to improve the efficiency of hydrogen production by water splitting [1-3]. On the electrode side, the use of non-platinum high efficiency electrode materials for water splitting will provide a promising future for the hydrogen economy. An ideal electrode for water electrolysis should have good permeability to water and gas. It should also offer good electrical properties with a long life. A porous graphite plate, when coated with titania, for example, is known to provide a simple and economical electrode for water electrolysis [4]. © 2010 IEEE.

The influence of 1D, meso- and crystal structures on charge transport and recombination in solid-state dye-sensitized solar cells

We have prepared single crystalline SnO2 and ZnO nanowires and polycrystalline TiO2 nanotubes (1D networks) as well as nanoparticle-based films (3D networks) from the same materials to be used as photoanodes for solid-state dye-sensitized solar cells. In general, superior photovoltaic performance can be achieved from devices based on 3-dimensional networks, mostly due to their higher short circuit currents. To further characterize the fabricated devices, the electronic properties of the different networks were measured via the transient photocurrent and photovoltage decay techniques. Nanowire-based devices exhibit extremely high, light independent electron transport rates while recombination dynamics remain unchanged. This indicates, contrary to expectations, a decoupling of transport and recombination dynamics. For typical nanoparticle-based photoanodes, the devices are usually considered electron-limited due to the poor electron transport through nanocrystalline titania networks. In the case of the nanowire-based devices, the system becomes limited by the organic hole transporter used. In the case of polycrystalline TiO2 nanotube-based devices, we observe lower transport rates and higher recombination dynamics than their nanoparticle-based counterparts, suggesting that in order to improve the electron transport properties of solid-state dye-sensitized solar cells, single crystalline structures should be used. These findings should aid future design of photoanodes based on nanowires or porous semiconductors with extended crystallinity to be used in dye-sensitized solar cells. © 2013 The Royal Society of Chemistry.

Field emission from TiO2/Ti nanotube arrays with different morphologies

Well-aligned TiO2/Ti nanotube arrays were electrochemically formed in a HF solution for different anodization times. Field emission scanning electron microscopy (FE-SEM) images reveal that anodization time had a great influence on the morphology of TiO2/Ti nanotube arrays. The composition of resulting nanotubes was analyzed by X-ray photoelectron spectroscopy (XPS). Field emission properties of the prepared samples with different morphologies were investigated by the Fowler-Nordheim (F-N) theory. The results indicate that the morphology can affect field emission behaviors. TiO2/Ti nanotube arrays with clear, uniform, and short nanotubes display moderate field emission properties, and have the better turn-on field of 4.6 V/mu m and good field emission stability. (C) 2010 Elsevier B.V. All rights reserved.

Enhance the optical absorptivity of nanocrystalline TiO2 film with high molar extinction coefficient ruthenium sensitizers for high performance dye-sensitized solar cells

We report two new heteroleptic polypyridyl ruthenium complexes, coded C101 and C102, with high molar extinction coefficients by extending the pi-conjugation of spectator ligands, with a motivation to enhance the optical absorptivity of mesoporous titania film and charge collection yield in a dye-sensitized solar cell. On the basis of this C101 sensitizer, several DSC benchmarks measured under the air mass 1.5 global sunlight have been reached.

New Efficiency Records for Stable Dye-Sensitized Solar Cells with Low-Volatility and Ionic Liquid Electrolytes

We report a high molar extinction coefficient heteroleptic polypyridyl ruthenium sensitizer, featuring an electron-rich 3,4-ethylenedioxythiophene unit in its ancillary ligand. A nanocrystalline titania film stained with this sensitizer shows an improved optical absorption, which is highly desirable for practical dye-sensitized solar cells with a thin photoactive layer, facilitating the efficient charge collection.

New Organic Sensitizer for Stable Dye-Sensitized Solar Cells with Solvent-Free Ionic Liquid Electrolytes

We report a high molar extinction coefficient metal-free sensitizer composed of a triarylamine donor in combination with the 2-(2,2'-bithiophen-5-yl)acrylonitrile conjugation unit and cyanoacrylic acid as an acceptor. In conjugation with a volatile acetonitrile-based electrolyte or a solvent-free ionic liquid electrolyte, we have fabricated efficient dye-sensitized solar cells showing a corresponding 7.5% or 6.1% efficiency measured under the air mass 1.5 global sunlight. The ionic liquid cell exhibits excellent stability during a 1000 h accelerated test under the light-soaking and thermal dual stress. Intensity-modulated photocurrent and photovolatge spectroscopies were employed along with the transient photoelectrical decay measurements to detail the electron transport in the mesoporous titania films filled with these two electrolytes.

Hydrothermal Synthesis and High Photocatalytic Activity of 3D Wurtzite ZnSe Hierarchical Nanostructures

Novel 3D wurtzite ZnSe hierarchical nanostructures have been synthesized by a mild hydrothermal treatment. The as-prepared flowerlike nanostructures efficiently catalyze the photodegradation of methylene blue and ethyl violet present in aqueous solutions under UV light irradiation, exhibiting higher photocatalytic activity than the commercially available photocatalysts P25 and ZnSe microspheres. We also demonstrate that flowerlike morphology is important for the excellent photocatalytic activity.

N-Methyl-N-Allylpyrrolidinium Based Ionic Liquids for Solvent-Free Dye-Sensitized Solar Cells

We prepared four new ionic liquids consisting of N-methyl-N-allylpyrrolidinium cation in conjunction with anions including iodide, nitrate, thiocyanate, and dicyanamide, respectively, and measured their physical properties of density, viscosity, and conductivity. Owing to the relatively lower melting point of electroactive N-methyl-N-allylpyrrolidinium iodide, in combination with three other nonelectroactive ionic liquids, we could construct solvent-free electrolytes possessing high iodide concentrations for dye-sensitized solar cells. We correlated temperature-dependent electrolyte viscosity with molar conductivity and triiodide mobility through applying an empirical Walden's rule and a modified Stokes-Einstein equation, respectively. We have further found that these anions (nitrate, thiocyanate, and dicyanamide) have different influences on surface states and electron transport in the mesoporous titania film, resulting in different photovoltages and photocurrents of dye-sensitized solar cells.

Conjugation of Selenophene with Bipyridine for a High Molar Extinction Coefficient Sensitizer in Dye-Sensitized Solar Cells

A high molar extinction coefficient heteroleptic polypyridyl ruthenium sensitizer, featuring a conjugated electron-rich selenophene unit in its ancillary ligand, has been synthesized and demonstrated as an efficient sensitizer in dye-sensitized solar cells. A nanocrystalline titania film stained with this sensitizer shows improved optical absorptivity, which is highly desirable for dye-sensitized solar cells with a thin photoactive layer. With preliminary testing, this sensitizer has already achieved a high efficiency of 10.6% measured under the air mass 1.5 global conditions.

Dye-Sensitized Solar Cells with a High Absorptivity Ruthenium Sensitizer Featuring a 2-(Hexylthio)thiophene Conjugated Bipyridine

We conjugated 2-(hexylthio)thiophene with bipyridine to construct a new heteroleptic polypyridyl ruthenium sensitizer exhibiting a charge-transfer band at 550 nm with a molar extinction coefficient of 18.7 x 10(3) M-1 cm(-1). In contrast to its analogues Z907 and C101, a mesoporous titania film stained with this new sensitizer featured a short light absorption length, allowing for the use of a thin photoactive layer for efficient light-harvesting and conversion of solar energy to electricity. With a preliminary testing, we have reached 11.4% overall power conversion efficiency measured at the air mass 1.5 global conditions. Transient photoelectrical decays and electrical impedance spectra were analyzed to picture the intrinsic physics of temperature-dependent photovoltage and photocurrent.