Catalyst-free synthesis, morphology evaluation and photocatalytic properties of pristine and calcinated titanate nanorods

Titanate nanorods with high photocatalytic activity was successfully synthesized through a simple catalyst-free hydrothermal method. The photocatalytic degradation of a model organic dye (Reactive Red 198) was accelerated by the calcination of the nanorods prior the reaction. The calcination of nanorods did not modify their morphology, however the crystallinity of the samples was significantly improved. Therefore, the quality of the samples is a key parameter determining their activity in the investigated photocatalytic process. The as-produced and annealed catalysts were characterized by high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), Diffuse Reflectance (DR) UV-Vis and resonance Raman spectroscopy.     

Ethanol combustion over strontium- and cerium-doped LaCoO3 catalysts

Ce- or Sr-doped LaCoO₃ bulk perovskites were prepared by citric acid method as well as 10 wt.% of LaCoO₃ was deposited on alumina carrier stabilized with lanthanum. Properties of prepared materials were characterized by determination of surface area, acid-basic properties and XRD, XPS, TPDO₂, H₂-TPR measurements as well as catalytic activity and selectivity for ethanol combustion was tested. It was found that substitution of La in LaCoO₃ with either Sr or Ce has only small effect on its activity in ethanol combustion. Strontium inserted into LaCoO₃ structure increases basic character of the perovskite surface as well as selectivity to acetaldehyde (ACA). Substitution of La with cerium has no effect on the concentration of basic sites and does not affect the selectivity to ACA. Activity of LaCoO₃-based catalysts in ethanol combustion and their selectivity to ACA formation can be explained on the basis of the presence of both -oxygen species and sites with basic character on the material surface.

Acid-basic properties of supported LaCoO₃ are dominated by acidic character of the carrier. Results of XPS and H₂-TPR measurements of LaCoO₃ supported on La–Al₂O₃ suggest that perovskite remains in strong interaction with carrier and probably is partially decomposed. Deposition of perovskite on stabilized carrier significantly increases the rate of ethanol combustion.     

The kinetics of phenol decomposition under UV irradiation with and without H2O2 on TiO2, Fe–TiO2 and Fe–C–TiO2 photocatalysts

H₂O₂ used in the photo-Fenton reaction with iron catalyst can accelerate the oxidation of Fe²⁺ to Fe³⁺ under UV irradiation and in the dark (in the so called dark Fenton process). It was proved that conversion of phenol under UV irradiation in the presence of H₂O₂ predominantly produces highly hydrophilic products and catechol, which can accelerate the rate of phenol decomposition. However, while H₂O₂ under UV irradiation could decompose phenol to highly hydrophilic products and dihydroxybenzenes in a very short time, complete mineralization proceeded rather slowly. When H₂O₂ is used for phenol decomposition in the presence of TiO₂ and Fe–TiO₂, decrease of OH radicals formed on the surface of TiO₂ and Fe–TiO₂ has been observed and photodecomposition of phenol is slowed down. In case of phenol decomposition under UV irradiation on Fe–C–TiO₂ photocatalyst in the presence of H₂O₂, marked acceleration of the decomposition rate is observed due to the photo-Fenton reactions: Fe²⁺ is likely oxidized to Fe³⁺, which is then efficiently recycled to Fe²⁺ by the intermediate products formed during phenol decomposition, such as hydroquinone (HQ) and catechol.     

Predicting the settling velocity of flocs formed in water treatment using multiple fractal dimensions

Here we introduce a distribution of floc fractal dimensions as opposed to a single fractal dimension value into the floc settling velocity model developed in earlier studies. The distribution of fractal dimensions for a single floc size was assumed to cover a range from 1.9 to 3.0. This range was selected based on the theoretically determined fractal dimensions for diffusion-limited and cluster-cluster aggregation. These two aggregation mechanisms are involved in the formation of the lime softening flocs analyzed in this study. Fractal dimensions were generated under the assumption that a floc can have any value of normally distributed fractal dimensions ranging from 1.9-3.0. A range of settling velocities for a single floc size was calculated based on the distribution of fractal dimensions. The assumption of multiple fractal dimensions for a single floc size resulted in a non-unique relationship between the floc size and the floc settling velocity, i.e., several different settling velocities were calculated for one floc size. The settling velocities calculated according to the model ranged from 0 to 10 mm/s (average 2.22 mm/s) for the majority of flocs in the size range of 1-250 μm (average 125 μm). The experimentally measured settling velocities of flocs ranged from 0.1 to 7.1 mm/s (average 2.37 mm/s) for the flocs with equivalent diameters from 10 μm to 260 μm (average 124 μm). Experimentally determined floc settling velocities were predicted well by the floc settling model incorporating distributions of floc fractal dimensions calculated based on the knowledge of the mechanisms of aggregation, i.e., cluster-cluster aggregation and diffusion-limited aggregation.     

Urinary mercury in adults in Poland living near a chloralkali plant

We conducted a study within the framework of the interdisciplinary European Mercury Emission from Chloralkali Plants (EMECAP) project to assess exposure to mercury (Hg) and the contribution of Hg emissions from a mercury cell chloralkali plant to urinary mercury (U-Hg) in adults living near the plant. We collected data from questionnaires and first morning urine samples from 75 subjects living near the Tarnow plant in Poland and 100 subjects living in a reference area. Median U-Hg was 0.32 mug/g creatinine (microg/gC) and 0.20 microg/gC, respectively. The median U-Hg was also higher in the amalgam-free subjects living near the plant (0.26 microg/gC) than in the reference group (0.18 microg/gC), but no such association was found in a multivariate analysis. There was a statistically significant positive association between U-Hg and number of teeth with amalgams, a negative association with age and a tendency towards higher U-Hg in female subjects. In the amalgam-free subjects there were statistically significant effects of female sex and fish consumption, and a negative association with age. The additional long-term average air Hg concentration from the plant, based on EMECAP environmental measurements and modelling, was estimated to be 1-3.5 ng/m(3) for the residential study area and should have a very small effect on U-Hg. The other Hg emission sources such as coal combustion facilities located nearby should be taken into account in assessing the overall impact of air Hg on U-Hg in this area.     

Synthesis and photocatalytic performance of TiO<Subscript>2</Subscript> nanospheres–graphene nanocomposite under visible and UV light irradiation

In this article, we present a fast and simple method to produce TiO₂ nanospheres–graphene nanocomposite with high photocatalytic activity under visible and UV light irradiation. TiO₂ nanospheres were adsorbed on graphene in sol–gel process. First, titanium (IV) butoxide underwent hydrolysis in graphene oxide (GO) ethanol solution resulting in TiO₂ nanospheres deposition on GO. Next, the material was calcinated to generate the phase transition of TiO₂ into anatase and reduce GO to graphene. The detailed characterization of the material was performed via transmission electron microscopy, energy dispersive X-rays spectrometer, Fourier-transformed infrared spectroscopy, X-ray diffraction, and Raman spectroscopy. Interestingly, the band-gap energy of the prepared photocatalyst was drastically decreased in comparison with the commercial photocatalyst P25 from 3.05 to 2.36 eV. This influenced in the activation of the material under visible light and resulted in high photocatalytic activity in the process of phenol decomposition in visible and UV irradiation.     

Optimization of evaporative fluid coolersOptimisation des refroidisseurs de liquide évaporatifs

In the paper the optimization of geometrical and operating parameters for evaporative fluid coolers has been presented. The algorithm of optimizational calculations contains:

• the mathematical model of heat and mass transfer in evaporative fluid coolers;

• model of operating costs based, among others, on the Zalewski–Gryglaszewski relations developed by the authors for evaluation of air pressure drops in the heat exchanger;

• model of evaporative heat exchangers production costs.

Optimization problem formulated for non-linear objective functions with inequality and equality constraints has been solved using Schittkowski's method based on quadratic programming. Two optimization problems have been considered. A solution to the first problem consists in the design of a heat exchanger with such geometrical parameters which ensure its maximum heat capacity at minimal total costs. A result to the second optimization problem are such thermal and flow parameters which will ensure minimum operating costs.The results of optimization calculations presented in the paper are accompanied by their experimental verification.     

Fabrication of biocompatible hydrogel coatings for implantable medical devices using Fenton-type reaction

In this paper the authors present a simple method of coating polyurethane (PU) surface with poly(vinyl pirrolidone) (PVP) hydrogel. The hydrogel-coated materials were designed for use in biomedical applications, especially in blood-contacting devices. The coating is formed due to free radical macromolecular grafting–crosslinking. Polymer surface was first immersed in an organic solution containing radical source: cumene hydroperoxide (CHP) with an addition of a branching and anchoring agent: ethylene glycol dimethylacrylate (EGDMA). In the second step, the substrate was immersed in a water solution containing given concentration of PVP and Fe²⁺. The novelty of the process consists in the fact that free radicals are formed mostly at the polymer/solution interface, what assures high grafting efficiency together with the formation of covalent bonds between polymer substrate and modifying layer.The process was optimized for reagents concentrations. The coating properties: thickness and the swelling ratio were strongly influenced by CHP, Fe²⁺, PVP and EGMDA concentrations. The chemical composition of the surface analyzed with FTIR-ATR spectroscopy confirmed the presence of PVP coating. In vitro biocompatibility tests with L929 fibroblasts confirmed non-cytotoxicity of the coatings. Hydrogel coating significantly improved polyurethane hemocompatibility. Studies with human whole blood revealed that both, the platelet consumption and the level of platelet activation were as low as for negative control.