Application of TiO2 Supported on Nickel Foam for Limitation of NOx in the Air via Photocatalytic Processes.

TiO2 was loaded on the porous nickel foam from the suspended ethanol solution and used for the photocatalytic removal of NOx. Such prepared material was heat-treated at various temperatures (400-600 °C) to increase the adhesion of TiO2 with the support. Obtained TiO2/nickel foam samples were characterized by XRD, UV-Vis/DR, FTIR, XPS, AFM, SEM, and nitrogen adsorption at 77 K. Photocatalytic tests of NO abatement were performed in the rectangular shape quartz reactor, irradiated from the top by UV LED light with an intensity of 10 W/m2. For these studies, a laminar flow of NO in the air (1 ppm) was applied under a relative humidity of 50% and a temperature of 28 °C. Concentrations of both NO and NO2 were monitored by a chemiluminescence NO analyzer. The adsorption of nitrogen species on the TiO2 surface was determined by FTIR spectroscopy. Performed studies revealed that increased temperature of heat treatment improves adhesion of TiO2 to the nickel foam substrate, decreases surface porosity, and causes removal of hydroxyl and alcohol groups from the titania surface. The less hydroxylated surface of TiO2 is more vulnerable to the adsorption of NO2 species, whereas the presence of OH groups on TiO2 enhances the adsorption of nitrate ions. Adsorbed nitrate species upon UV irradiation and moisture undergo photolysis to NO2. As a consequence, NO2 is released into the atmosphere, and the efficiency of NOx removal is decreasing. Photocatalytic conversion of NO to NO2 was higher for the sample heated at 400 °C than for that at 600 °C, although coverage of nickel foam by TiO2 was lower for the former one. It is stated that the presence of titania defects (Ti3+) at low temperatures of its heating enhances the adsorption of hydroxyl groups and the formation of hydroxyl radicals, which take part in NO oxidation. Contrary to that, the presence of titania defects in TiO2 through the formation of ilmenite structure (NiTiO3) in TiO2/nickel foam heated at 600 °C inhibits its photocatalytic activity. No less, the sample obtained at 600 °C indicated the highest abatement of NOx due to the high and stable adsorption of NO2 species on its surface.

Impact of TiO2 Reduction and Cu Doping on Bacteria Inactivation under Artificial Solar Light Irradiation.

Preparation of TiO2 using the hydrothermal treatment in NH4OH solution and subsequent thermal heating at 500-700 °C in Ar was performed in order to introduce some titania surface defects. The highest amount of oxygen vacancies and Ti3+ surface defects were observed for a sample heat-treated at 500 °C. The presence of these surface defects enhanced photocatalytic properties of titania towards the deactivation of two bacteria species, E. coli and S. epidermidis, under artificial solar lamp irradiation. Further modification of TiO2 was targeted towards the doping of Cu species. Cu doping was realized through the impregnation of the titania surface by Cu species supplied from various copper salts in an aqueous solution and the subsequent heating at 500 °C in Ar. The following precursors were used as a source of Cu: CuSO4, CuNO3 or Cu(CH3COO)2. Cu doping was performed for raw TiO2 after a hydrothermal process with and without NH4OH addition. The obtained results indicate that Cu species were deposited on the titania surface defects in the case of reduced TiO2, but on the TiO2 without NH4OH modification, Cu species were attached through the titania adsorbed hydroxyl groups. Cu doping on TiO2 increased the absorption of light in the visible range. Rapid inactivation of E. coli within 30 min was obtained for the ammonia-reduced TiO2 heated at 500 °C and TiO2 doped with Cu from CuSO4 solution. Photocatalytic deactivation of S. epidermidis was greatly enhanced through Cu doping on TiO2. Impregnation of TiO2 with CuSO4 was the most effective for inactivation of both E. coli and S. epidermidis.

Enhanced Degradation of Ethylene in Thermo-Photocatalytic Process Using TiO2/Nickel Foam.

The photocatalytic decomposition of ethylene was performed under UV-LED irradiation in the presence of nanocrystalline TiO2 (anatase, 15 nm) supported on porous nickel foam. The process was conducted in a high-temperature chamber with regulated temperature from ambient to 125 °C, under a flow of reacted gas (ethylene in synthetic air, 50 ppm, flow rate of 20 mL/min), with simultaneous FTIR measurements of the sample surface. Ethylene was decomposed with a higher efficiency at elevated temperatures, with a maximum of 28% at 100-125 °C. The nickel foam used as support for TiO2 enhanced ethylene decomposition at a temperature of 50 °C. However, at 50 °C, the stability of ethylene decomposition was not maintained in the following reaction run, but it was at 100 °C. Photocatalytic measurements conducted in the presence of certain radical scavengers indicated that a higher efficiency of ethylene decomposition was obtained due to the improved separation of charge carriers and the increased formation of superoxide anionic radicals, which were formed at the interface of the thermally activated nickel foam and TiO2.

The Superiority of TiO2 Supported on Nickel Foam over Ni-Doped TiO2 in the Photothermal Decomposition of Acetaldehyde.

Acetaldehyde decomposition was performed under heating at a temperature range of 25-125 °C and UV irradiation on TiO2 doped by metallic Ni powder and TiO2 supported on nickel foam. The process was carried out in a high-temperature reaction chamber, "The Praying MantisTM", with simultaneous in situ FTIR measurements and UV irradiation. Ni powder was added to TiO2 in the quantity of 0.5 to 5.0 wt%. The photothermal measurements of acetaldehyde decomposition indicated that the highest yield of acetaldehyde conversion on TiO2 and UV irradiation was obtained at 75 °C. The doping of nickel to TiO2 did not increase its photocatalytic activity. Contrary to that, the application of nickel foam as a support for TiO2 appeared to be highly advantageous because it increased the decomposition of acetaldehyde from 31 to 52% at 25 °C, and then to 85% at 100 °C in comparison with TiO2 itself. At the same time, the mineralization of acetaldehyde to CO2 doubled in the presence of nickel foam. However, oxidized nickel foam used as support for TiO2 was detrimental. Most likely, different mechanisms of electron transfer between Ni-TiO2 and NiO-TiO2 occurred. The application of nickel foam greatly enhanced the separation of free carriers in TiO2. As a consequence, high yields from the photocatalytic reactions were obtained.

Sulphated TiO2 Reduced by Ammonia and Hydrogen as an Excellent Photocatalyst for Bacteria Inactivation.

This study presents a relatively low-cost method for modifying TiO2-based materials for photocatalytic bacterial inactivation. The photocatalytic inactivation of Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus epidermidis) bacteria using modified sulphated TiO2 was studied. The modification focused on the reduction of TiO2 by ammonia agents and hydrogen at 400-450 °C. The results showed a high impact of sulphate species on the inactivation of E. coli. The presence of these species generated acid sites on TiO2, which shifted the pH of the reacted titania slurry solution to lower values, around 4.6. At such a low pH, TiO2 was positively charged. The ammonia solution caused the removal of sulphate species from TiO2. On the other hand, hydrogen and ammonia molecules accelerated the removal of sulphur species from TiO2, as did heating it to 450 °C. Total inactivation of E. coli was obtained within 30 min of simulated solar light irradiation on TiO2 heat-treated at 400 °C in an atmosphere of Ar or NH3. The S. epidermidis strain was more resistant to photocatalytic oxidation. The contact of these bacteria with the active titania surface is important, but a higher oxidation force is necessary to destroy their cell membrane walls because of their thicker cell wall than E. coli. Therefore, the ability of a photocatalyst to produce ROS (reactive oxidative species) will determine its ability to inactivate S. epidermidis. An additional advantage of the studies presented is the inactivation of bacteria after a relatively short irradiation time (30 min), which does not often happen with photocatalysts not modified with noble metals. The modification methods presented represent a robust and inexpensive alternative to photocatalytic inactivation of bacteria.

Effect of Nano-SiO2 on the Microstructure and Mechanical Properties of Concrete under High Temperature Conditions.

The aim of the research was to determine how the admixture of nanosilica affects the structure and mechanical performance of cement concrete exposed to high temperatures (200, 400, 600, and 800 °C). The structural tests were carried out on the cement paste and concrete using the methods of thermogravimetric analysis, mercury porosimetry, and scanning electron microscopy. The results show that despite the growth of the cement matrix's total porosity with an increasing amount of nanosilica, the resistance to high temperature improves. Such behavior is the result of not only the thermal characteristics of nanosilica itself but also of the porosity structure in the cement matrix and using the effective method of dispersing the nanostructures in concrete. The nanosilica densifies the structure of the concrete, limiting the number of the pores with diameters from 0.3 to 300 µm, which leads to limitation of the microcracks, particularly in the coarse aggregate-cement matrix contact zone. This phenomenon, in turn, diminishes the cracking of the specimens containing nanosilica at high temperatures and improves the mechanical strength.

Immobilization of TiO2 and Fe-C-TiO2 photocatalysts on the cotton material for application in a flow photocatalytic reactor for decomposition of phenol in water.

TiO2 and Fe-C-TiO2 photocatalysts have been immobilized on the cotton material and used in a flow photocatalytic reactor for phenol decomposition. The cotton material has been applied as a support for photocatalyst, because can be easily removed and replaced in a reactor, what facilitates the performance of the photocatalytic process. Fe-C-TiO2 photocatalyst has been prepared by modification of TiO2 fine particles of anatase structure with FeC2O4 through heating in Ar at 500 degrees C. The immobilized photocatalysts could efficiently decompose phenol in multiple use, Fe-C-TiO2 showed higher photocatalytic activity than TiO2, around 15-18 mg and 15-16 mg of phenol have been decomposed after 5 h of UV irradiation on Fe-C-TiO2 and TiO2, respectively. After addition of H2O2 the phenol decomposition and the mineralization degree have been accelerated, especially with immobilized Fe-C-TiO2 photocatalyst, in case of that the photo-Fenton reaction occurred. In the presence of H2O2 around 26-28 mg and 21-24 mg of phenol have been decomposed on Fe-C-TiO2 and TiO2 respectively, after 5 h of UV irradiation.

Application of carbon-coated TiO2 for decomposition of methylene blue in a photocatalytic membrane reactor.

An application of carbon-coated TiO(2) for decomposition of methylene blue (MB) in a photocatalytic membrane reactor (PMR), coupling photocatalysis and direct contact membrane distillation (DCMD) was investigated. Moreover, photodegradation of a model pollutant in a batch reactor without membrane distillation (MD) was also examined. Carbon-modified TiO(2) catalysts containing different amount of carbon and commercially available TiO(2) (ST-01) were used in this study. The carbon-coated catalyst prepared from a mixture of ST-01 and polyvinyl alcohol in the mass ratio of 70/30 was the most effective in degradation of MB from all of the photocatalysts applied. Photodecomposition of MB on the recovered photocatalysts was lower than on the fresh ones. The photodegradation of MB in the PMR was slower than in the batch reactor, what probably resulted from shorter time of exposure of the catalyst particles to UV irradiation. The MD process could be successfully applied for separation of photocatalyst and by-products from the feed solution.

Effect of the carbon coating in Fe-C-TiO(2) photocatalyst on phenol decomposition under UV irradiation via photo-Fenton process.

Fe-C-TiO(2) photocatalysts which contained the residue carbon (0.2-3.3 mass%) were prepared from a mixture of TiO(2) and FeC(2)O(4) through the heating at 673-1173 K in Ar. These photocatalysts did not show a high adsorption of phenol, but they were active in photo-Fenton reactions during decomposition of phenol under UV irradiation with addition of H(2)O(2). It was proved that Fe(2+) governed the photoactivity of Fe-C-TiO(2) photocatalysts, it decreased with heat-treatment temperature above 773 K. For comparison, Fe-TiO(2) photocatalyst was prepared by heating TiO(2) and FeC(2)O(4) at 823 K in air for 3h. Phenol decomposition was going much slower on Fe-TiO(2) photocatalyst in comparison with Fe-C-TiO(2), of which mechanism was different, on the former phenol was decomposed by the radical reaction, on the latter through a complex reaction with iron and intermediates of phenol decomposition. Therefore carbon-coating TiO(2) was found to be advantageous for mounting iron and its application for the phenol decomposition via photo-Fenton process.

Dependence of photocatalytic activity of anatase powders on their crystallinity.

Structural changes in anatase phase in four TiO(2) photocatalysts with annealing at high temperatures were followed by evaluating crystallite size and lattice strain of anatase phase separately and measuring the content of anatase. The rate constant k for the decomposition of methylene blue in its aqueous solution under UV irradiation was determined as a measure of photocatalytic activity. Marked dependences in crystallinity improvement, i.e., the growth of crystallite and the decrease in lattice strain, and in phase transformation from anatase to rutile phases of TiO(2) on annealing temperature was observed above 500 degrees C, depending on starting photocatalysts used. The phase transformation to rutile started after reaching of crystallite size to about 32 nm and of lattice strain to about 0.5 x 10(-3). Rate constant k was found to depend on both crystallite size and lattice strain of anatase; it increased with increasing crystallite size up to about 32 nm and decreasing lattice strain down to about 0.5 x 10(-3). Further increase in crystallite size and decrease in lattice strain induced the decrease in rate constant k, mainly due to the partial transformation of anatase to rutile. The present results showed that the activity of the photocatalysts was possible to be improved by annealing at a high temperature, by selecting an optimal condition of annealing for getting a high crystallinity in anatase phase and no phase transformation to rutile phase.