Although the nitrous oxide belongs among three of the most contributing greenhouse gases to global warming, it is quite neglected by photocatalytic society. The g-C3N4 and WO3 composites were therefore tested for the photocatalytic decomposition of N2O for the first time. The pure photocatalysts were prepared by simple calcination of precursors, and the composites were prepared by mixing of suspension of pure components in water followed by calcination. The structural (X-ray diffraction, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy), textural (N2 physisorption), and optical properties (diffuse reflectance spectroscopy, photoluminescence spectroscopy, photoelectrochemical measurements) of all composites were correlated with photocatalytic activity. The experimental results and results from characterization techniques confirmed creation of Z-scheme in the WO3/g-C3N4 composites, which was confirmed by hydroxyl radicals' trapping measurements. The photocatalytic decomposition of N2O was carried out in the presence of UVA light (peak intensity at 365 nm) and the 1:2 WO3/g-C3N4 composite was the most active one, but the photocatalytic activity was just negligibly higher than that of pure WO3. This is caused by relatively weak interaction between WO3 and g-C3N4 which was revealed from XPS.

• Klíčová slova
• Heterojunction, N2O decomposition, OH trapping, Photocatalysis, WO3, g-C3N4,
• MeSH
• chemické modely MeSH
• difrakce rentgenového záření MeSH
• fotochemické procesy * MeSH
• fotoelektronová spektroskopie MeSH
• hydroxylový radikál MeSH
• katalýza MeSH
• oxid dusičitý chemie   MeSH
• světlo MeSH
• transmisní elektronová mikroskopie MeSH
• wolfram chemie   MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• hydroxylový radikál MeSH
• oxid dusičitý MeSH
• wolfram MeSH

Cu-Al-O x mixed metal oxides with intended molar ratios of Cu/Al = 85/15, 78/22, 75/25, 60/30, were prepared by thermal decomposition of precursors at 600 °C and tested for the decomposition of nitrous oxide (deN2O). Techniques such as XRD, ICP-MS, N2 physisorption, O2-TPD, H2-TPR, in situ FT-IR and XAFS were used to characterize the obtained materials. Physico-chemical characterization revealed the formation of mixed metal oxides characterized by different specific surface area and thus, different surface oxygen default sites. The O2-TPD results gained for Cu-Al-O x mixed metal oxides conform closely to the catalytic reaction data. In situ FT-IR studies allowed detecting the form of Cu+⋯N2 complexes due to the adsorption of nitrogen, i.e. the product in the reaction between N2O and copper lattice oxygen. On the other hand, mostly nitrate species and NO were detected but those species were attributed to the residue from catalyst synthesis.

• Publikační typ
• časopisecké články MeSH

Iron-containing zeolite-based catalysts play a pivotal role in environmental processes aimed at mitigating the release of harmful greenhouse gases, such as nitrous oxide (N2O) and methane (CH4). Despite the rich iron chemistry in zeolites, only a fraction of iron species that exhibit an open coordination sphere and possess the ability for electron transfer are responsible for activating reagents. In addition, the splitting of molecular oxygen is facilitated by bare iron cations embedded in zeolitic matrices. Mössbauer spectroscopy is the ideal tool for investigating the valency and geometry of iron species in zeolites because it leaves no iron forms silent and provides insights into in-situ processes. This review is dedicated to the utilization of Mössbauer spectroscopy to elucidate the nature of the extra-framework iron centers in ferrierite (FER), beta-structured (*BEA), and ZSM-5 zeolite (MFI) zeolites, which are active in N2O decomposition and CH4 oxidation through using the active oxygen derived from N2O and O2. In this work, a structured summary of the Mössbauer parameters established over the last two decades is presented, characterizing the specific iron active centers and intermediates formed upon iron's interaction with N2O/O2 and CH4. Additionally, the impact of preparation methods, iron loading, and the long-term stability on iron speciation and its redox behavior under reaction conditions is discussed.

• Klíčová slova
• Mössbauer spectroscopy, N2O decomposition, iron sites, methane, zeolites,
• Publikační typ
• časopisecké články MeSH
• přehledy MeSH

The study is focused on the testing of the photocatalytic ability to decompose nitrous oxide (N₂O) over cordierite/CeO² nanoparticles ceramic photocatalysts. The activity of ceramic materials was compared with the activity of industrially produced TiO² (Evonik photocatalyst). Photocatalytic decomposition of N₂O over the ceramic samples and the TiO² Evonik was performed in annular batch reactor illuminated with 8 W Hg lamp (λ ═ 254 nm wavelength). Reaction kinetics was well described by pseudo 1st rate law. Photocatalytic activity of cordierite/CeO² was better in comparison with TiO² Evonik P25. The highest N₂O conversion (56%) after 20 h of irradiation in inert gas was achieved over the sample with higher amount of CeO². This photocatalyst sample was examined for photocatalytic activity in the decomposition of N₂O in the three various gaseous feed mixtures. The gaseous feed mixtures were: N₂O enriched with O² (6.5 mol.%); N₂O enriched with H₂O(25 mol.%) and N₂O enriched with mixture of O² and H₂O(6.5 mol.% and 25 mol.%, respectively). It is assumed that the reduced conversion of N₂O (47%) observed in the flow of the mixture of N₂O and H₂Ocould be affected by the sorption of water vapor on/onto the photocatalyst "active sites" causing less penetration of light and thus reducing the efficiency of photocatalytic decomposition of N2O. The presence of oxygen in the N₂O mixture had only little effect to photocatalytic decomposition of N₂O.

• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH

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.

• Publikační typ
• časopisecké články MeSH

This paper focuses on tetraamminecopper(II) perchlorate (TACP), a relatively newly used and popular homemade explosive that is insufficiently described in the literature. The compound was analyzed using commonly used forensic laboratory techniques such as FTIR, Raman, XRPD, and DTA. The TACP molecule was labeled with four 15N atoms on ammonia ligands to assign vibrational modes to the resulting bands. The paper also describes the thermal decomposition of TACP using thermoanalytical methods TGA/MS. The TACP decomposes to the final product CuO in six distinct ranges, releasing N2O, NO, HCl, O2, H2O, and NH3. It has been found that TACP is not a stable compound and will decompose spontaneously to ammonia, ammonium perchlorate, and basic copper perchlorate within a few months if exposed to air at room temperature. Residues of precursors have been detected in TACP prepared by four improvised preparation methods published on the Internet. These residues can be used to identify the precursor used in the preparation. The post-blast residues of TACP are of ordinary shape, but the use of TACP as an explosive can be indicated by the presence of a high content of copper and chlorine atoms in post-blast residues. The results of canine detection of TACP indicate that the dog is able to detect TACP, but the dog is likely to focus on the smell of ammonia in the TACP odor.

• Klíčová slova
• FTIR, Forensic analysis, Powder diffraction, Raman spectroscopy, TACP, Tetraamminecopper(II) perchlorate,
• Publikační typ
• časopisecké články MeSH