Nanocrystalline TiO2 and halloysite clay mineral composite films prepared by sol-gel method:Synergistic effect and the case of silver modification to the photocatalytic degradation of basic blue- 41 azo dye in water

Tubular halloysite clay mineral and nanocrystalline TiO2 were incorporated in the preparation of nanocomposite films on glass substrates via sol-gel method at 450 °C. The synthesis involves a simple chemical method employing nonionic surfactant molecule as pore directing agent along with the acetic acid-based sol-gel route without addition of water molecules. Drying and thermal treatment of composite films ensure elimination of organic material and lead to the formation of TiO2 nanoparticles homogeneously distributed on the surface of the halloysite. Nanocomposite films without cracks of active anatase crystal phase and small crystallite size on halloysite nanotubes are characterized by microscopy techniques and porosimetry methods in order to examine their structural properties. The composite halloysite-TiO2 films with variable quantities of halloysite were examined as photocatalysts to the discoloration of Basic Blue 41 azo dye in water. These nanocomposite films proved to be very promising photocatalysts and highly effective to dye's discoloration in spite of small amount of halloysite/TiO2 catalyst immobilized onto glass substrates. It also has been shown that the efficiency of the halloysite/TiO2 films could be further improved when silver particles were deposited on their surface after successful adsorption from an aqueous solution of a silver salt and UV reduction of the adsorbed ions

Influence of electrolyte co-additives on the performance of dye-sensitized solar cells

The presence of specific chemical additives in the redox electrolyte results in an efficient increase of the photovoltaic performance of dye-sensitized solar cells (DSCs). The most effective additives are 4-tert-butylpyridine (TBP), N-methylbenzimidazole (NMBI) and guanidinium thiocyanate (GuNCS) that are adsorbed onto the photoelectrode/electrolyte interface, thus shifting the semiconductor's conduction band edge and preventing recombination with triiodides. In a comparative work, we investigated in detail the action of TBP and NMBI additives in ionic liquid-based redox electrolytes with varying iodine concentrations, in order to extract the optimum additive/I2 ratio for each system. Different optimum additive/I2 ratios were determined for TBP and NMBI, despite the fact that both generally work in a similar way. Further addition of GuNCS in the optimized electrolytic media causes significant synergistic effects, the action of GuNCS being strongly influenced by the nature of the corresponding co-additive. Under the best operation conditions, power conversion efficiencies as high as 8% were obtained

Fabrication of Porous TiO2 Hollow Spheres and Their Application in Gas Sensing

In this work, porous TiO2 hollow spheres with an average diameter of 100 nm and shell thickness of 20 nm were synthesized by a facile hydrothermal method with NH4HCO3 as the structure-directing agent, and the formation mechanism for this porous hollow structure was proved to be the Ostwald ripening process by tracking the morphology of the products at different reaction stages. The product was characterized by SEM, TEM, XRD and BET analyses, and the results show that the as-synthesized products are anatase phase with a high surface area up to 132.5 m2/g. Gas-sensing investigation reveals that the product possesses sensitive response to methanal gas at 200°C due to its high surface area

Preparation of TiO2 Anatase Nanocrystals by TiCl4 Hydrolysis with Additive H2SO4

A new methodology was developed to synthesize uniform titania anatase nanocrystals by the hydrolysis of titanium chloride in sulfuric acid aqueous solutions at 0–90°C. The samples were characterized by Raman spectroscopy, UV-visible spectroscopy, transmission electron microscopy (TEM), electron diffraction (ED), and an Energy dispersive X-ray spectroscopy (EDS). The effects of the reaction temperature, mole ratio of SO42− to Ti4+, and the calcinations temperature on the particle size and crystal phase were investigated. Depending on the acidity, the hydrolysis temperature, and the calcination temperature, rhombic anatase nanocrystals sizes in the range of 10 nm to 50 nm were obtained. In the additive of sulfuric acid, Raman spectra and electron diffraction confirmed that the nanoparticles are composed of anatase TiO2. No other titania phases, such as rutile or brookite, were detected

Age-dependent alterations in the inflammatory response to pulmonary challenge

The aging lung is increasingly susceptible to infectious disease. Changes in pulmonary physiology and function are common in older populations, and in those older than 60 years, pneumonia is the major cause of infectious death. Understanding age-related changes in the innate and adaptive immune systems, and how they affect both pulmonary and systemic responses to pulmonary challenge are critical to the development of novel therapeutic strategies for the treatment of the elderly patient. In this observational study, we examined age-associated differences in inflammatory responses to pulmonary challenge with cell wall components from Gram-positive bacteria. Thus, male Sprague-Dawley rats, aged 6 months or greater than 18 months (approximating humans of 20 and 55-65 years), were challenged, intratracheally, with lipoteichoic acid and peptidoglycan. Cellular and cytokine evaluations were performed on both bronchoalveolar lavage fluid (BAL) and plasma, 24 h post-challenge. The plasma concentration of free thyroxine, a marker of severity in non-thyroidal illness, was also evaluated. The older animals had an increased chemotactic gradient in favor of the airspaces, which was associated with a greater accumulation of neutrophils and protein. Furthermore, macrophage migration inhibitory factor (MIF), an inflammatory mediator and putative biomarker in acute lung injury, was increased in both the plasma and BAL of the older, but not young animals. Conversely, plasma free thyroxine, a natural inhibitor of MIF, was decreased in the older animals. These findings identify age-associated inflammatory/metabolic changes following pulmonary challenge that it may be possible to manipulate to improve outcome in the older, critically ill patient

sensitized solar cells

A series of three heteroleptic ruthenium complexes containing 2,2'-bipyridine-4,4'-dicarboxamide ligands with different substituents (propyl, benzyl or 2-phenylethyl) was synthesized as possible sensitizers for dye sensitized solar cells (DSSCs). Their structure was characterized with H-1 NMR and FTIR while their optical and electrochemical properties were also investigated. The observed optical differences were associated to structural properties of the three complexes and different electron donor strength of the ancillary ligands. In particular, ruthenium complex with propyl based ligand showed higher molar extinction coefficient succeeding better light harvesting. Semitransparent dye sensitized solar cells employing quasi-solid-state electrolyte and the three ruthenium complexes were constructed under the same fabrication conditions and electrically characterized under standard conditions of light irradiance (100 mW/cm(2), AM 1.5). Their behavior was compared with that of commercially available ruthenium complex D907 with increased conjugation length of the ancillary ligand, in terms of current- voltage characteristic curves under simulated solar light and in the dark while electrochemical impedance spectroscopy was also used for local resistance to charge transfer across the TiO2-dye/electrolyte interface. The influence of ancillary ligands into ruthenium complexes was discussed in terms of the cells' efficiency. A maximum overall performance of 5.0% was monitored for ruthenium complex with propyl substituent in comparison to 5.1% that was measured for semitransparent quasi-solid state devices with commercial D907. (C) 2018 Elsevier B.V. All rights reserved

Photophysical properties of an amphiphilic cationic hemicyanine dye in solution and adsorbed on a TiO2 mesoporous film

The photophysical behavior of the amphiphilic cationic hemicyanine dye N-n-heptyl-4-(((dimethylamino)phenyl)ethenyl)pyridinium bromide (H7HC) has been examined in various environments with the intention to assess its state of adsorption on a TiO2 mesoporous film. In some solvents, such as short-chain alcohols or chloroform, the dye is dissolved as a monomer. In other solvents, like water and cyclohexane, it is found in concentration-dependent aggregate forms. H7HC monomer absorption and fluorescence spectra show a symmetric solvatochromic effect previously found for other amphiphilic hemicyanines (Fromherz, P. J. Phys. Chem., 1995, 99, 7188). Aggregates are of the H-type; i.e., they are formed by repulsive interaction and display a hypsochromic shift in their absorption spectra. When adsorbed on nanostructured mesoporous TiO2 films, H7HC is found in aggregate form, which evolves in the course of time by displaying a hypsochromic shift in the absorption maximum. Photoelectrochemical studies with an ITO-TiO2-H7HC electrode revealed that aggregates are responsible for the ability of the dye to photosensitize TiO2

New bipyridine ruthenium dye complexes with amide based ancillary ligands as sensitizers in semitransparent quasi-solid-state dye sensitized solar cells

A series of three heteroleptic ruthenium complexes containing 2,2′-bipyridine-4,4′-dicarboxamide ligands with different substituents (propyl, benzyl or 2-phenylethyl) was synthesized as possible sensitizers for dye sensitized solar cells (DSSCs). Their structure was characterized with 1H NMR and FTIR while their optical and electrochemical properties were also investigated. The observed optical differences were associated to structural properties of the three complexes and different electron donor strength of the ancillary ligands. In particular, ruthenium complex with propyl based ligand showed higher molar extinction coefficient succeeding better light harvesting. Semitransparent dye sensitized solar cells employing quasi-solid-state electrolyte and the three ruthenium complexes were constructed under the same fabrication conditions and electrically characterized under standard conditions of light irradiance (100 mW/cm2, AM 1.5). Their behavior was compared with that of commercially available ruthenium complex D907 with increased conjugation length of the ancillary ligand, in terms of current–voltage characteristic curves under simulated solar light and in the dark while electrochemical impedance spectroscopy was also used for local resistance to charge transfer across the TiO2-dye/electrolyte interface. The influence of ancillary ligands into ruthenium complexes was discussed in terms of the cells’ efficiency. A maximum overall performance of 5.0% was monitored for ruthenium complex with propyl substituent in comparison to 5.1% that was measured for semitransparent quasi-solid state devices with commercial D907. © 2018 Elsevier B.V