Antibacterial, Antifungal and Ecotoxic Effects of Ammonium and Imidazolium Ionic Liquids Synthesized in Microwaves.

Ionic liquids are increasingly used for their superior properties. Four water-immiscible ionic liquids (butyltriethylammonium bis(trifluoromethylsulfonyl)imide, octyltriethylammonium bis(trifluoromethylsulfonyl)imide, dodecyltriethylammonium bis(trifluoromethylsulfonyl)imide, butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) and their water miscible precursors (bromides) were synthesized in a microwave reactor and by conventional heating. The best conditions for microwave-assisted synthesis concerning the yield and the purity of the product are proposed. The heating in the microwave reactor significantly shortened the reaction time. Biocide and ecotoxic effects of synthesized ionic liquids and their precursors were investigated. All tested compounds had at least a little effect on the growth or living of microorganisms (bacteria or mold). The precursor dodecyltriethylammonium bromide was found to be the strongest biocide, but posed a risk to the aquatic environment due to its relatively high EC50 value in the test with Vibrio fischeri. We assumed that apart from the alkyl chain length, the solubility in water, duration of action, or type of anion can influence the final biocide and ecotoxic effect.

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.

Catalytic Oxidation of Ammonia over Cerium-Modified Copper Aluminium Zinc Mixed Oxides.

Copper-containing mixed metal oxides are one of the most promising catalysts of selective catalytic oxidation of ammonia. These materials are characterized by high catalytic efficiency; however, process selectivity to dinitrogen is still an open challenge. The set of Cu-Zn-Al-O and Ce/Cu-Zn-Al-O mixed metal oxides were tested as catalysts of selective catalytic oxidation of ammonia. At the low-temperature range, from 250 °C up to 350 °C, materials show high catalytic activity and relatively high selectivity to dinitrogen. Samples with the highest Cu loading 12 and 15 mol.% of total cation content were found to be the most active materials. Additional sample modification by wet impregnation of cerium (8 wt.%) improves catalytic efficiency, especially N2 selectivity. The comparison of catalytic tests with results of physicochemical characterization allows connecting the catalysts efficiency with the form and distribution of CuO on the samples' surface. The bulk-like well-developed phases were associated with sample activity, while the dispersed CuO phases with dinitrogen selectivity. Material characterization included phase composition analysis (X-ray powder diffraction, UV-Vis diffuse reflectance spectroscopy), determination of textural properties (low-temperature N2 sorption, scanning electron microscopy) and sample reducibility analysis (H2 temperature-programmed reduction).

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).