Role of lamp type in conventional batch and micro-photoreactor for photocatalytic hydrogen production.

The use of an irradiation source with a homogeneous distribution of irradiation in the volume of the reaction mixture belongs to the essential aspects of heterogeneous photocatalysis. First, the efficacy of six lamps with various radiation intensity and distribution characteristics is contrasted. The topic of discussion is the photocatalytic hydrogen production from a methanol-water solution in the presence of a NiO-TiO2 photocatalyst. The second section is focused on the potential of a micro-photoreactor system-the batch reactor with a micro-reactor with a circulating reaction mixture, in which the photocatalytic reaction takes place using TiO2 immobilized on borosilicate glass. Continuous photocatalytic hydrogen generation from a methanol-water solution is possible in a micro-photoreactor. This system produced 333.7 ± 21.1 µmol H2 (252.8 ± 16.0 mmol.m-2, the hydrogen formation per thin film area) in a reproducible manner during 168 h.

Chicken Cartilage-Derived Carbon for Efficient Xylene Removal.

Chicken cartilage was used for the first time as a raw material for the microwave-assisted synthesis of biochar and activated carbon. Various microwave absorbers, i.e., commercial active carbon, scrap tyres, silicon carbide, and chicken bone-derived biochar, as well as various microwave powers, were tested for their effect on the rate of pyrolysis and the type of products formed. Biochars synthesised under 400 W in the presence of scrap tyres and chicken bone-derived biochar were activated with KOH and K2CO3 with detergent to produce activated carbon with a highly developed porous structure that would be able to effectively adsorb xylene vapours. All carbons were thoroughly characterised (infrared spectroscopy, X-ray fluorescence spectrometry, nitrogen adsorption/desorption, Raman spectroscopy, proximate and ultimate analysis) and tested as xylene sorbents in dynamic systems. It was found that the activation causes an increase of up to 1042 m2·g-1 in the specific surface area, which ensures the sorption capacity of xylene about 300 mg·g-1. Studies of the composition of biogas emitted during pyrolysis revealed that particularly valuable gaseous products are formed when pyrolysis is carried out in the presence of silicon carbide as a microwave absorber.

Oxidation of Methanol and Dichloromethane on TiO2-CeO2-CuO, TiO2-CeO2 and TiO2-CuO@VUKOPOR®A Ceramic Foams.

The application-attractive form of TiO2, CeO2 and CuO-based open-cell foam supported catalysts was designed to investigate their catalytic performance in oxidation of two model volatile organic compounds-methanol and dichloromethane. TiO2-CeO2, TiO2-CuO and TiO2-CeO2-CuO catalysts as thin films were deposited on VUKOPOR®A ceramic foam using a reverse micelles-controlled sol-gel method, dip-coating and calcination. Three prepared catalytic foams were investigated via light-off tests in methanol and dichloromethane oxidation in the temperature range of 45-400 °C and 100-500 °C, respectively, at GHSV of 11, 600 h-1, which fits to semi-pilot/industrial conditions. TiO2-CuO@VUKOPOR®A foam showed the best catalytic activity and CO2 yield in methanol oxidation due to its low weak Lewis acidity, high weak basicity and easily reducible CuO species and proved good catalytic stability within 20 h test. TiO2-CeO2-CuO@VUKOPOR®A foam was the best in dichloromethane oxidation. Despite of its lower catalytic activity compared to TiO2-CeO2@VUKOPOR®A foam, its highly-reducible -O-Cu-Ce-O- active surface sites led to the highest CO2 yield and the highest weak Lewis acidity contributed to the highest HCl yield. This foam also showed the lowest amount of chlorine deposits.

Leaching of metals from red mud and toxicity in human cells in vitro.

Toxicity of red mud, a waste from alumina production, was studied using human breast cancer MCF-7 cells. Culture medium was prepared by mixing water for 3 days with the red mud and removing solid particles afterwards (red mud water). Culture for 48 h of the cells in this medium in neutral pH decreased the cell viability, as analyzed by the MTT-test, and increased the formation of reactive oxygen species. Thus, neutralization does not eliminate the toxicity of red mud. In preliminary experiments, a combined effect of five metals (Cr, Li, V, Al, As) increased the formation of ROS (reactive oxygen species) statistically significantly. Each element separately did not have a similar effect. In environmental applications, red mud is likely to be used after activation. In this work, the red mud was activated using hydrochloric acid to study the physical and chemical properties before and after the treatment. Activation increased the specific surface area of red mud from 16 m2 g-1 to 148 m2 g-1, which is beneficial in many environmental applications such as in the adsorptive removal of pollutants. After activation, leaching of some elements from the red mud decreased (e.g. Al from 38.0 to 0.56 mg L-1, As from 21.0 to 2.1 µg L-1, V from 172.0 to 29.8 µg L-1) while some increased (e.g. Li from 0.04 to 2.81 mg L-1, Cr from 0.35 to 3.23 mg L-1).

Effects of Structure and Composition of Adsorbents on Competitive Adsorption of Gaseous Emissions: Experiment and Modeling.

Dangerous gases arising from combustion processes must be removed from the air simply and cheaply, e.g., by adsorption. This work is focused on competitive adsorption experiments and force field-based molecular modeling of the interactions at the molecular level. Emission gas, containing CO, NO, SO2, and CO2, was adsorbed on activated carbon, clay mineral, silicon dioxide, cellulose, or polypropylene at two different temperatures. At 20 °C, activated carbon had the highest NO and SO2 adsorption capacity (120.83 and 3549.61 µg/g, respectively). At 110 °C, the highest NO and SO2 adsorption capacity (6.20 and 1182.46 µg/g, respectively) was observed for clay. CO was adsorbed very weakly, CO2 not at all. SO2 was adsorbed better than NO, which correlated with modeling results showing positive influence of carboxyl and hydroxyl functional groups on the adsorption. In addition to the wide range of adsorbents, the main novelty of this study is the modeling strategy enabling the simulation of surfaces with pores of controllable sizes and shapes, and the agreement of the results achieved by this strategy with the results obtained by more computationally demanding methods. Moreover, the agreement with experimental data shows the modeling strategy to be a valuable tool for further adsorption studies.

Hematites Precipitated in Alkaline Precursors: Comparison of Structural and Textural Properties for Methane Oxidation.

Hematite (α-Fe2O3) catalysts prepared using the precipitation methods was found to be highly effective, and therefore, it was studied with methane (CH4), showing an excellent stable performance below 500 °C. This study investigates hematite nanoparticles (NPs) obtained by precipitation in water from the precursor of ferric chloride hexahydrate using precipitating agents NaOH or NH4OH at maintained pH 11 and calcined up to 500 °C for the catalytic oxidation of low concentrations of CH4 (5% by volume in air) at 500 °C to compare their structural state in a CH4 reducing environment. The conversion (%) of CH4 values decreasing with time was discussed according to the course of different transformation of goethite and hydrohematites NPs precursors to magnetite and the structural state of the calcined hydrohematites. The phase composition, the size and morphology of nanocrystallites, thermal transformation of precipitates and the specific surface area of the NPs were characterized in detail by X-ray powder diffraction, transmission electron microscopy, infrared spectroscopy, thermal TG/DTA analysis and nitrogen physisorption measurements. The results support the finding that after goethite dehydration, transformation to hydrohematite due to structurally incorporated water and vacancies is different from hydrohematite α-Fe2O3. The surface area SBET of Fe2O3_NH-70 precipitate composed of protohematite was larger by about 53 m2/g in comparison with Fe2O3_Na-70 precipitate composed of goethite. The oxidation of methane was positively influenced by the hydrohematites of the smaller particle size and the largest lattice volume containing structurally incorporated water and vacancies.

Isokinetic leg muscle strength relationship to dynamic balance reflects gymnast-specific differences in adolescent females.

Balance, together with other motor qualities, plays an important role in the successful execution of specific gymnastic skills. However, it is also not clear whether different demands on dynamic balance and power produced by lower limb can be observed in sport-specific differences among gymnasts of various modalities. The question also is as to what extent isokinetic leg muscle strength contributes to anterior and posterior postural stability in gymnasts. Therefore, the aim of the study was i) to compare variables of dynamic balance and isokinetic leg muscle strength in rhythmic, artistic, and aerobic gymnasts, and ii) to investigate the relationship of reach distances in anterior, posteromedial, and posterolateral directions, as well as the composite score in the Y-balance test with an isokinetic muscle strength during knee extension and flexion at different velocities in female gymnasts of various disciplines. Altogether seven aerobic, five artistic, and six rhythmic gymnasts performed the Y-balance test and isokinetic leg muscle strength test at 60°/s, 180°/s, and 300°/s. Results showed significant between-group differences in the composite score in the Y-balance test of the dominant (F = 3.536, p = .041) and non-dominant symmetry (F = 4.804, p = .015). Similarly, average power produced during knee extension and knee flexion at 60°/s, 180°/s and 300°/s differed significantly among these groups (all at p˂0.05). In addition, there was a significant relationship between the composite score of the dominant limb symmetry and isokinetic dominant limb extension strength at 60°/s (r = .54), 180°/s (r = .87), and 300°/s (r = .84) in aerobic gymnasts. The composite score of the dominant limb symmetry was also associated with isokinetic dominant limb extension strength, albeit only at 60°/s in both artistic (r = .60) and rhythmic gymnasts (r = .55). Such between-group differences may be ascribed to their different demands on maintenance of balance under dynamic conditions and leg muscle power within their sport specializations. Taking into account significant association between the dominant limb symmetry and isokinetic dominant limb extension strength, it may be concluded that both muscle strength and fast speeds contribute to dynamic balance in adolescent gymnasts.

Effect of Nanoparticle Size in Pt/SiO2 Catalyzed Nitrate Reduction in Liquid Phase.

Effect of platinum nanoparticle size on catalytic reduction of nitrate in liquid phase was examined under ambient conditions by using hydrogen as a reducing agent. For the size effect study, Pt nanoparticles with sizes of 2, 4 and 8 nm were loaded silica support. TEM images of Pt nanoparticles showed that homogeneous morphologies as well as narrow size distributions were achieved during the preparation. All three catalysts showed high activity and were able to reduce nitrate below the recommended limit of 50 mg/L in drinking water. The highest catalytic activity was seen with 8 nm platinum; however, the product selectivity for N2 was highest with 4 nm platinum. In addition, the possibility of PVP capping agent acting as a promoter in the reaction is highlighted.

A Case Study of Waste Scrap Tyre-Derived Carbon Black Tested for Nitrogen, Carbon Dioxide, and Cyclohexane Adsorption.

Waste scrap tyres were thermally decomposed at the temperature of 600 °C and heating rate of 10 °C·min-1. Decomposition was followed by the TG analysis. The resulting pyrolytic carbon black was chemically activated by a KOH solution at 800 °C. Activated and non-activated carbon black were investigated using high pressure thermogravimetry, where adsorption isotherms of N2, CO2, and cyclohexane were determined. Isotherms were determined over a wide range of pressure, 0.03-4.5 MPa for N2 and 0.03-2 MPa for CO2. In non-activated carbon black, for the same pressure and temperature, a five times greater gas uptake of CO2 than N2 was determined. Contrary to non-activated carbon black, activated carbon black showed improved textural properties with a well-developed irregular mesoporous-macroporous structure with a significant amount of micropores. The sorption capacity of pyrolytic carbon black was also increased by activation. The uptake of CO2 was three times and for cyclohexane ten times higher in activated carbon black than in the non-activated one. Specific surface areas evaluated from linearized forms of Langmuir isotherm and the BET isotherm revealed that for both methods, the values are comparable for non-activated carbon black measured by CO2 and for activated carbon black measured by cyclohexane. It was found out that the N2 sorption capacity of carbon black depends only on its specific surface area size, contrary to CO2 sorption capacity, which is affected by both the size of specific surface area and the nature of carbon black.

Successful Immobilization of Lanthanides Doped TiO2 on Inert Foam for Repeatable Hydrogen Generation from Aqueous Ammonia.

We describe the successful possibility of the immobilization of a photocatalyst on foam, which is beneficial from a practical point of view. An immobilized photocatalyst is possible for use in a continuous experiment and can be easily separated from the reactor after the reaction concludes. Parent TiO2, La/TiO2, and Nd/TiO2 photocatalysts (containing 0.1 wt.% of lanthanide) were prepared by the sol-gel method and immobilized on Al2O3/SiO2 foam (VUKOPOR A) by the dip-coating method. The photocatalysts were investigated for the photocatalytic hydrogen generation from an aqueous ammonia solution under UVA light (365 nm). The evolution of hydrogen was compared with photolysis, which was limited to zero. The higher hydrogen generation was observed in the presence of 0.1 wt.% La/TiO2 than in 0.1 wt.% Nd/TiO2. This is, besides other things, related to the higher level of the conduction band, which was observed for 0.1 wt.% La/TiO2. The higher conduction band's position is more effective for hydrogen production from ammonia decomposition.

Epidemiology of Competition Injuries in Elite European Judo Athletes: A Prospective Cohort Study.

OBJECTIVE: To determine the injury incidence rate (IIR) and injury pattern, and to identify risk factors for injury, among elite adult European judo athletes. DESIGN: Prospective cohort study. SETTING: The 2015 Under 23 European Judo Championships, Bratislava, Slovakia. PARTICIPANTS: All registered athletes (N = 295). INDEPENDENT VARIABLES: Sex, weight division, and fight outcome. MAIN OUTCOME MEASURES: Injury incidence rates were calculated per 1000 athlete-exposures (IIRAE) and per 1000 minutes of exposure (IIRME) with 95% confidence intervals (CI). Subgroups were compared by calculating the injury incidence rate ratio (RR) with a 95% CI. RESULTS: The overall IIRAE and IIRME were 35.6 (95% CI, 22.8-53.0) and 10.9 (95% CI, 7.0-16.2), respectively. The most frequently injured anatomical region was the head/neck (41%), whereas the most common type of injury was contusion (33%). The risk of injury was almost 4 times greater for defeated athletes compared with winners [RRME 3.80 (95% CI, 1.47-9.82)]. Athletes in middleweight divisions had a greater risk of injury compared with their lightweight [RRME 3.58 (95% CI, 1.24-10.35)] and heavyweight [RRME 2.34 (95% CI, 0.93-5.89)] counterparts. The risk of injury for women was not significantly different from their male counterparts [RRME 1.33 (95% CI, 0.61-2.90)]. CONCLUSIONS: Weight division (middle) and fight outcome (losing) are significant risk factors for injury. The IIR in elite adult judo competition is lower than that in taekwondo and karate. Future research is encouraged to investigate the actual severity of judo injuries, and to investigate potentially modifiable risk factors to mitigate the risk of injury in judo.

TiO2 and Nitrogen Doped TiO2 Prepared by Different Methods; on the (Micro)structure and Photocatalytic Activity in CO2 Reduction and N2O Decomposition.

TiO2 as nanostructured powders were prepared by (1) sol-gel process and (2) hydrothermal method in combination with (A) the processing by pressurized hot water and methanol or (B) calcination. The subsequent synthesis step was the modification of prepared nanostructured TiO2 with nitrogen using commercial urea. Textural, structural, surface and optical properties of prepared TiO2 and N/TiO2 were characterized by nitrogen physisorption, powder X-ray diffraction, X-ray photoelectron spectroscopy and DR UV-vis spectroscopy. It was revealed that TiO2 and N/TiO2 processed by pressurized fluids showed the highest surface areas. Furthermore, all prepared materials were the mixtures of major anatase phase and minor brookite phase, which was in nanocrystalline or amorphous (as nuclei) form depending on the applied preparation method. All the N/TiO2 materials exhibited enhanced crystallinity with a larger anatase crystallite-size than undoped parent TiO2. The photocatalytic activity of the prepared TiO2 and N/TiO2 was tested in the photocatalytic reduction of CO2 and the photocatalytic decomposition of N2O. The key parameters influencing the photocatalytic activity was the ratio of anatase-to-brookite and character of brookite. The optimum ratio of anatase-to-brookite for the CO2 photocatalytic reduction was determined to be about 83 wt.% of anatase and 17 wt.% of brookite (amorphous-like) (TiO2-SG-C). The presence of nitrogen decreased a bit the photocatalytic activity of tested materials. On the other hand, TiO2-SG-C was the least active in the N2O photocatalytic decomposition. In the case of N2O photocatalytic decomposition, the modification of TiO2 crystallites surface by nitrogen increased the photocatalytic activity of all investigated materials. The maximum N2O conversion (about 63 % after 18 h of illumination) in inert gas was reached over all N/TiO2.

Nd/TiO2 Anatase-Brookite Photocatalysts for Photocatalytic Decomposition of Methanol.

Neodymium enriched TiO2 anatase-brookite powders were prepared by unconventional method via using pressurized hot fluids for TiO2 crystallization and purification. The photocatalysts were tested in the CH3OH photocatalytic decomposition and they were characterized with respect to the textural (nitrogen adsorption), structural (XRD, XPS, and Raman spectroscopies), chemical (XRF), and optical (DR UV-Vis spectroscopy) and photoelectrochemical measurement. All prepared materials were nanocrystalline, had biphasic (anatase- brookite) structure and relatively large specific surface area (125 m2.g-1). The research work indicates that the doping of neodymium on TiO2 photocatalysts significantly enhances the efficiency of photocatalytic reaction. The photocatalytic activity increased with increasing portion of hydroxyl oxygen to the total amount of oxygen species. It was ascertained that the optimal amount of 1 wt% Nd in TiO2 accomplished the increasing of hydrogen production by 70% in comparison with pure TiO2. The neodymium doped on the titanium dioxide act as sites with accumulation of electrons. The higher efficiency of photocatalytic process was achieved due to improved electron-hole separation on the modified TiO2 photocatalysts. This result was confirmed by electrochemical measurements, the most active photocatalysts proved the highest photocurrent responses.

Photocatalytic decomposition of methanol over La/TiO2 materials.

Lanthanum-modified TiO2 photocatalysts (0.2-1.5 wt% La) were investigated in the methanol decomposition in an aqueous solution. The photocatalysts were prepared by the common sol-gel method followed by calcination. The structural (X-ray diffraction, Raman, X-ray photoelectron spectroscopy), textural (N2 physisorption), and optical properties (diffuse reflectance spectroscopy, photoelectrochemical measurements) of all synthetized nanomaterials were correlated with photocatalytic activity. Both pure TiO2 and La-doped TiO2 photocatalysts proved higher yields of hydrogen in comparison to photolysis. The photocatalyst with optimal amount of lanthanum (0.2 wt% La) showed almost two times higher amount of hydrogen produced at the same time as in the presence of pure TiO2. The photocatalytic activity increased with both increasing photocurrent response and decreasing amount of lattice and surface O species. It has been shown that both direct and indirect mechanisms of methanol photocatalytic oxidation participate in the production of hydrogen. Both direct and indirect mechanisms take part in the formation of hydrogen.

Novel TiO2/C3N4 Photocatalysts for Photocatalytic Reduction of CO2 and for Photocatalytic Decomposition of N2O.

TiO2/g-C3N4 photocatalysts with the ratio of TiO2 to g-C3N4 ranging from 0.3/1 to 2/1 were prepared by simple mechanical mixing of pure g-C3N4 and commercial TiO2 Evonik P25. All the nanocomposites were characterized by X-ray powder diffraction, UV-vis diffuse reflectance spectroscopy, photoluminescence, X-ray photoelectron spectroscopy, Raman spectroscopy, infrared spectroscopy, transmission electron microscopy, photoelectrochemical measurements, and nitrogen physisorption. The prepared mixtures along with pure TiO2 and g-C3N4 were tested for the photocatalytic reduction of carbon dioxide and photocatalytic decomposition of nitrous oxide. The pure g-C3N4 exhibited the lowest photocatalytic activity in both cases, pointing to a very high recombination rate of charge carriers. On the other hand, the most active photocatalyst toward all the products was (0.3/1)TiO2/g-C3N4. The highest activity is achieved by combination of a number of factors: (i) specific surface area, (ii) adsorption edge energy, (iii) crystallite size, and (iv) efficient separation of the charge carriers, where the efficient charge separation is the most decisive parameter.

Microstructure, Optical and Photocatalytic Properties of TiO2 Thin Films Prepared by Chelating-Agent Assisted Sol-Gel Method.

Single and multilayer TiO2 thin films coated on two types of soda-lime glass substrates (microscope slides and cylinders) were prepared by a chelating agent-assisted sol-gel method, using ethyl acetoacetate as a chelating agent, dip-coating and calcination at 500 °C for 2 h in air. Phase composition, microstructural, morphological and optical properties of thin films were comprehensively investigated by using XRF, advanced XRD analysis, Raman and UV-vis spectroscopy and AFM. It was found out that the thickness of thin films increases linearly with increasing number of deposited layers, indicating a good adhesion of the titania solution to a glass substrate as well as to a previously calcined layer. 1 layer film crystallized to anatase-TiO2(B) mixture with minor/negligible amount of nanosized brookite, 2-4 layers films crystallized to anatase-brookite-TiO2(B) mixture. In contrast to other multilayers films, 4 layers film was highly inhomogeneous. The different phase composition of thin films was clarified based on the crystallization via titanate/s and metastable monoclinic TiO2(B) as a consequence of several phenomena; the diffusion of Na⁺ ions from a soda-lime glass substrate, acidic conditions and repeated thermal treatment. The multilayer films were in average highly transparent (80-95%) in the visible light region with the sharp absorption edge in the UV light region. Additionally, the photocatalytic properties of selected multilayer films were compared in AO7 photodegradation. Photocatalytic experiments showed that thicker 4 layers film of tricrystalline anatase-brookite-TiO2(B) phase mixture was similarly active as thinner 3 layers film of similar phase composition, which may be a consequence of the inhomogeneity of the thicker film.

Photocatalytic Hydrogen Formation from Ammonia in an Aqueous Solution Over Pt-Enriched TiO2-ZrO2 Photocatalyst.

The aim of this study was to remove ammonia from an aqueous solution by its decomposition to valuable products such as H2 and harmless N2 under UV light. The decomposition of ammonia by photocatalytic process represents an emerging and interesting way of its removal since beside the need of its reduction from the drinking and wastewaters with the respect to its negative impact on human and mammals health, it can lead to generation of hydrogen as an alternative fuel. A laboratory-synthesized Pt/TiO2-ZrO2 photocatalyst was studied and its photocatalytic activity was compared with the activity of commercial TiO2 Evonik P25. The Pt/TiO2-ZrO2 photocatalyst was prepared by combining a sol-gel process controlled within reverse micelles of nonionic surfactant Triton X-114 in cyclohexane, impregnation under vacuum and calcination. Explored photocatalysts were characterized by organic elementary analysis, nitrogen physisorption, XRD, FESEM and UV-Vis spectroscopy. The real platinum content in the Pt/TiO2-ZrO2 photocatalyst was determined by ICP-MS. The photocatalytic decomposition of ammonia was investigated in the time range of 0-12 h. During the first two hours the generation of hydrogen was almost negligible. The generation of hydrogen increased after 4 h of irradiation. Based on time dependences of ammonia decomposition the kinetic rate constants for Pt/TiO2-ZrO2 and TiO2 Evonik P25 photocatalysts were calculated. The ammonia photocatalytic decomposition was described well by the first order kinetic equation. The photocatalytic ammonia decomposition over the platinized TiO2-ZrO2 photocatalyst was proving 2 times higher photocatalytic performance than Evonik P25 (1241 µmol/g(cat) and 665 µmol/g(cat), respectively).