Marcel Šihor

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.

Investigation of low Ce amount doped-TiO2 prepared by using pressurized fluids in photocatalytic N2O decomposition and CO2 reduction

Ce doped TiO2 anatase/brookite composites with 0.6–5.5 wt% of Ce, as well as parent TiO2 anatase/brookite were synthesized to be investigated in two environmentally-beneficial reactions, the photocatalytic decomposition of N2O and the photocatalytic reduction of CO2. Composites were prepared unconventionally, by using sol–gel method combined with the processing by pressurized hot fluids (in the sequence water/methanol/water). The physicochemical and electronic properties of all synthesized composites were characterized by organic elementary analysis, nitrogen physisorption, powder X-ray diffraction, X-ray fluorescence spectroscopy, diffuse reflectance UV-vis spectroscopy and work function measurements. It was revealed that all composites show comparable textural properties, crystallite size, as well as optical properties, except for the 5.5 wt% Ce/TiO2 composite which showed significantly lowered band gap energy due to the significantly higher population of Ce. Concerning the composite structural properties, the addition of different amounts of Ce in the range of 0.6–5.5 wt% affected markedly the phase composition of composites, namely the anatase-to-brokite weight ratio. Concerning the photocatalytic tests the 5.5 wt% Ce/TiO2 composite showed the highest photocatalytic performance. The highest photocatalytic performance of the 5.5 wt% Ce/TiO2 composite can be attributed to the lowest composite work function which is affected by both the amount of Ce, as well as the phase composition.Graphical Abstract

Influence of Reaction Medium on CO2 Photocatalytic Reduction Yields Over Zns-MMT / Vliv Reakčního Prostření Na Výtěžky Fotokatalytické Redukce CO2 V Přítomnosti Zns-MMT

Abstract The reduction of CO2 by photocatalysts is one of the most promising methods since CO2 can be reduced to useful compounds by irradiating it with UV light at room temperature and ambient pressure. The aim of this work was to assess the effect of a reaction media on CO2 photocatalytic reduction yields over ZnS nanoparticles deposited on montmorillonite (ZnS-MMT). Four different reaction media, such as NaOH, NaOH+Na2SO3 (1:1), NH4OH, NH4OH+Na2SO3 (1:1), were tested. The pure sodium hydroxide was better than ammonium hydroxide for the yields of the both gas phase (CH4 and CO) and liquid phase (CH3OH). The addition of Na2SO3 improved methanol yields due to the oxidation prevention of incipient methanol to carbon dioxide. The gas phase yields were decreased by the Na2SO3 addition. The best tested reaction medium for the photocatalytic reduction of CO2 was the solution of sodium hydroxide. Abstrakt Redukce CO2 pomocí fotokatalyzátorů je jedna z nejslibnějších metod, jelikož CO2 může být redukován na užitečné sloučeniny ozařováním UV zářením při pokojové teplotě a tlaku. Tato práce byla zaměřena na posouzení vlivu reakčních prostředí na výtěžky fotokatalytické redukce CO2 v přítomnosti nanočástic ZnS nanesených na montmorillonit (ZnS-MMT). Byla testována čtyři různá reakční prostředí, NaOH, NaOH+Na2SO3 (1:1), NH4OH, NH4OH+Na2SO3 (1:1). Výtěžky v obou fázích, plynné (CH4 a CO) i kapalné (CH3OH), byly vyšší v čistém hydroxidu sodném než v hydroxidu amonném. Přídavek Na2SO3 zvýšil výtěžky methanolu a to díky zamezení oxidace vznikajícího methanolu zpět na oxid uhličitý. Výtěžky plynné fáze se však po přídavku Na2SO3 snížily. Nejlepším z testovaných reakčních prostředí pro fotokatalytickou redukci CO2 byl roztok hydroxidu sodného.