Study of Perovskite Type Oxide Catalysts for Partial Oxidation of Methane

Studium bylo provedeno na perovskitových systémech obecného vzorce A1-xA‘xB1-yB‘yO3± (A=La, Sm, A´=Ca, B´=Al, B=Co,Fe,Mn a Cr) . Zkoumané perovskitové oxidy byly syntetizovány polymeračními metodami a charakterizovány rentgenovou strukturní analýzou, BET, SEM a EDX. TPD spektra a katalytické testy byly provedeny ve vysokoteplotním reaktoru s pístovým tokem a analyza produktů provedena hmotnostním spektrometrem. Bylo zjištěno, že oxidace metanu při poměrech O2/CH40,5 silně závisí na teplotě. Při teplotách mezi 300-700oC dochází k úplné oxidaci metanu na oxid uhličitý a vodu, zatímco při teplotách nad 700oC probíhá parciální oxidace metanu (POM) na vodík a oxid uhelnatý (syngas). To je vysvětlováno rovnováhou O2 mezi plynnou fází a pevným perovskitem. Bylo použito osm perovskitových systémů, na kterých probíhají tyto reakce stejným způsobem. Reformace probíhá nad teplotu 700oC. Mezi nejlepší katalytické systémy patřily perovskity typu kobaltitu a feritu. Na základě získaných výsledků byl navržen pro oxidace a reformace perovskitovými systémy Mars van Krevelenův mechanismus. Bylo dokázáno, že POM probíhá dvoustupňovým mechanismem. V první kroku vznikají produkty úplné, totální oxidace (TO), které v druhém kroku přecházejí na syntézní plyn (H2+CO).Research was curried out on the perovskite systems with general formula A1-xA‘xB1-yB‘yO3± (where A=La, Sm, A´=Ca, B´=Al, B=Co,Fe,Mn and Cr). Perovskite oxides were sythesized by polymerisation methods and characterised by RTG analysis, BET method, SEM and EDX. TPD spectra and catalyst testing were measured in high temperature plug flow reactor and products were analysed by mass spectrometry. It was found, that metane oxidation at ratio O2/CH40,5 depended on the temperature. Total oxidation proceeded at the temperature betwen 300-700oC to the carbon dioxide and water, while the partial oxidation of metane (POM) occured at above 700oC to the hydrogen and carbon oxid (syngas). This was ascribed by equilibrium of O2 betwen gas phase and solid perovskite. There was used 12 perovskite systems, which catalysed methane oxidation by the same way. Dry reforming of methane run above temperature 700oC. Cobaltite and ferite type perovskites were found as the most active catalytic systems. On the base of obtained results the Mars van Krevelen mechanism was established for explanation of oxidation and reformation of methane by perovskite systems. It was showed, that POM was running by two steps mechanism. Products of total oxidation was occured in the first step, which were passed over to the syngas (H2+CO) in the second step.

Zirconia / Alumina Composite Foams with Calcium Phosphate Coating

In this study, mechanical properties of calcium phosphate foams were enhanced by zirconia/alumina porous cores prepared by polymer replica technique. This technique was chosen to ensure interconnected pores of optimal size for cell migration and attachment. The porosity of ZA cores (50 – 99%) was controlled by multistep impregnation process, the size of pore windows was 300 – 500 μm. Sintered ZA cores were impregnated by hydroxyapatite or β-tricalcium phosphate slurry to improve bioactivity. The bone like apatite layer was formed on coatings when immersed in a simulated body fluid. Neither of tested materials was cytotoxic. Thus, the composite foam can be potentially used as a permanent substitute of cancellous bone

Zirconia / Alumina Composite Foams with Calcium Phosphate Coating

In this study, mechanical properties of calcium phosphate foams were enhanced by zirconia/alumina porous cores prepared by polymer replica technique. This technique was chosen to ensure interconnected pores of optimal size for cell migration and attachment. The porosity of ZA cores (50 – 99%) was controlled by multistep impregnation process, the size of pore windows was 300 – 500 μm. Sintered ZA cores were impregnated by hydroxyapatite or β-tricalcium phosphate slurry to improve bioactivity. The bone like apatite layer was formed on coatings when immersed in a simulated body fluid. Neither of tested materials was cytotoxic. Thus, the composite foam can be potentially used as a permanent substitute of cancellous bone

The first solid-state route to luminescent Au(I)—glutathionate and its pH-controlled transformation into ultrasmall oligomeric Au10–12(SG)10–12 nanoclusters for application in cancer radiotheraphy

There is still a need for synthetic approaches that are much faster, easier to scale up, more robust and efficient for generating gold(I)–thiolates that can be easily converted into gold–thiolate nanoclusters. Mechanochemical methods can offer significantly reduced reaction times, increased yields and straightforward recovery of the product, compared to the solution-based reactions. For the first time, a new simple, rapid and efficient mechanochemical redox method in a ball-mill was developed to produce the highly luminescent, pH-responsive Au(I)–glutathionate, [Au(SG)]n. The efficient productivity of the mechanochemical redox reaction afforded orange luminescent [Au(SG)]n in isolable amounts (mg scale), usually not achieved by more conventional methods in solution. Then, ultrasmall oligomeric Au10–12(SG)10–12 nanoclusters were prepared by pH-triggered dissociation of [Au(SG)]n. The pH-stimulated dissociation of the Au(I)–glutathionate complex provides a time-efficient synthesis of oligomeric Au10–12(SG)10–12 nanoclusters, it avoids high-temperature heating or the addition of harmful reducing agent (e.g., carbon monoxide). Therefore, we present herein a new and eco-friendly methodology to access oligomeric glutathione-based gold nanoclusters, already finding applications in biomedical field as efficient radiosensitizers in cancer radiotherapy

Macroporous bioceramic scaffolds based on tricalcium phosphates reinforced with silica: microstructural, mechanical, and biological evaluation

The positive effect of silica on microstructural, mechanical and biological properties of calcium phosphate scaffolds was investigated in this study. Scaffolds containing 3D interconnected spherical macropores with diameters in the range of 300-770 mu m were prepared by the polymer replica technique. Reinforcement was achieved by incorporating 5 to 20 wt % of colloidal silica into the initial hydroxyapatite (HA) powder. The HA was fully decomposed into alpha and beta-tricalcium phosphate, and silica was transformed into cristobalite at 1200 degrees C. Silica reinforced scaffolds exhibited compressive strength in the range of 0.3 to 30 MPa at the total porosity of 98-40%. At a nominal porosity of 75%, the compressive strength was doubled compared to scaffolds without silica. When immersed into a cultivation medium, the formation of an apatite layer on the surfaces of scaffolds indicated their bioactivity. The supportive effect of the silicon enriched scaffolds was examined using three different types of cells (human adipose-derived stromal cells, L929, and ARPE-19 cells). The cells firmly adhered to the surfaces of composite scaffolds with no sign of induced cell death. Scaffolds were non-cytotoxic and had good biocompatibility in vitro. They are promising candidates for therapeutic applications in regenerative medicine

Mechanochemical synthesis of mononuclear gold(I) halide complexes of diphosphine ligands with tuneable luminescent properties

A mechanochemical method is reported for the synthesis of Au(diphos)X complexes of diphosphine (diphos = XantPhos and N-XantPhos) ligands and halide ions (X = Cl and I). The Au(XantPhos)X (1: X = Cl; 2: X = I) and Au(N-XantPhos)Cl (3) complexes exhibited either yellowish green (1) or bluish green (2) emission, whereas 3 was seemingly non-emissive in the solid state at room temperature. Blue- (2B) and bluish green (2G) luminescent concomitant solvates of 2 were obtained by recrystallization. Luminescent colour changes from blue (2B) or bluish green (2G) to yellow were observed when these forms were subjected to mechanical stimulus, while the original emission colour can be recovered in the presence of solvent vapours. Moreover, the luminescence of 2B can be reversibly altered between blue and yellow by heating/cooling-cycles. These results demonstrate the power of mechanochemistry in the rapid (4 min reaction time), efficient (up to 98% yield) and greener synthesis of luminescent and stimuli-responsive gold(I) complexes

Zirconia / Alumina Composite Foams with Calcium Phosphate Coating

In this study, mechanical properties of calcium phosphate foams were enhanced by zirconia/alumina porous cores prepared by polymer replica technique. This technique was chosen to ensure interconnected pores of optimal size for cell migration and attachment. The porosity of ZA cores (50 – 99%) was controlled by multistep impregnation process, the size of pore windows was 300 – 500 μm. Sintered ZA cores were impregnated by hydroxyapatite or β-tricalcium phosphate slurry to improve bioactivity. The bone like apatite layer was formed on coatings when immersed in a simulated body fluid. Neither of tested materials was cytotoxic. Thus, the composite foam can be potentially used as a permanent substitute of cancellous bone

Tištěné vzory oxidu titaničitého podpořeného organosilikátovou matricí připravené za studena

Preparation of photocatalytic active layers by cold-setting inkjet printing. Comparison of printed, UV-cured and sintered layers; their physical properties, as well as, photocatalytic and electrophotocatalytic properties.Příprava fotokatalyticky aktivních vrstev metodou inkjet printingu za studena. Srovnání vytištěných, UV-ošetřených a teplotně ošetřených vrstev; jejich fyzikálních vlastností, stejně jako fotokatalytických a elektrofotokatalytických vlastností

Heat treatment induced phase transformations in zirconia and yttriastabilized zirconia monolithic aerogels

Monolithic, structurally stable zirconia (ZrO2) aerogels can be used in high temperature applications and as medical implants. The macroscopic properties of these solids can be fine-tuned by the appropriate thermal treatment of the amorphous aerogels. Herein, we investigate the thermally induced phase transitions of ZrO2 and yttria-stabilized zirconia (YSZ) monolithic aerogels. All aerogels were produced by an acid-catalyzed sol-gel technique and subsequent supercritical drying (SCD). A complete reaction mechanism is proposed for the formation of the wet gel network. Also, the phase transformations taking place during calcination were followed as function of temperature by in-situ X-ray diffraction measurements. Composition and size of the forming crystallites were calculated from the XRD data. Phase transition is controlled by the temperature-dependent growth of crystallite size during calcination up to 1200 °C. Both tetragonal and monoclinic zirconia form in pure ZrO2 aerogels, and a single tetragonal phase forms in YSZ aerogels