Investigation of Co3O4 and LaCoO3 interaction by performing N2O decomposition tests under Co3O4-CoO transition temperature

The research presented in this paper addresses the question: How does the addition of a small amount of LaCoO3 impact the activity of a Co3O4 catalyst? By testing such a catalyst in N2O decomposition under conditions at which the thermal decomposition of Co3O4 to CoO is possible, one gains unique insight into how the two phases interact. The activity of such a catalyst increases in the entire studied temperature range, unlike the activity of the undoped cobalt catalyst which is lower at 850 °C than at 800 °C due to the reduction of Co3O4 to CoO. XRD measurements showed that CoO was also the main cobalt oxide present in the Co3.5La catalyst after operating at 850 °C, as did the XPS measurements, but there was no drop of activity associated with this change. The influence of NO, O2 and H2O on the activity of the new catalyst, Co3.5La, was determined. Lack of positive effect of NO, a known oxygen scavenger, on the activity was noticed at all temperatures, showing that the effect of LaCoO3 is probably due to increased oxygen desorption. Temperature programed oxidation (TPO) tests showed that the beneficial effects of the presence of LaCoO3 on the activity of cobalt oxide at 850 °C were probably caused by enhanced diffusion of O2− anions through the entire catalyst, which facilitates desorption of oxygen molecules from the surface

Application of potassium ion deposition in determining the impact of support reducibility on catalytic activity of au/ceria-zirconia catalysts in CO oxidation, NO oxidation, and C3H8 combustion

The purpose of the study was to show how a controlled, subtle change of the reducibility of the support by deposition of potassium ions impacts the activity of gold catalysts. Since the activity of supported gold catalysts in carbon monoxide oxidation is known to strongly depend on the reducibility of the support, this reaction was chosen as the model reaction. The results of tests conducted in a simple system in which the only reagents were CO and O2 showed good agreement with the CO activity trend in tests performed in a complex stream of reagents, which also contained CH4, C2H6, C3H8, NO, and water vapor. The results of the X-ray Diffraction (XRD) studies revealed that the support has the composition Ce0.85Zr0.15O2, that its lattice constant is the same for all samples, and that gold is mostly present in the metallic phase. The reducibility of the systems was established based on Temperature Programmed Reduction (TPR) and in situ XRD measurements in H2 atmosphere. The results show that the low temperature reduction peak, which is due to the presence of gold, is shifted to a higher value by the presence of 0.3 at% potassium ions on the surface. Moreover, the increase of the potassium loading leads to a more pronounced shift. The T50 of CO oxidation in the simple model stream was found to exhibit an excellent linear correlation with the maximum temperature of the low temperature reduction peak of Au catalysts. This means that stabilizing oxygen with a known amount of potassium ions can be numerically used to estimate the T50 in CO oxidation. The results in the complex stream also showed a similar dependence of CO conversion on reducibility, though there was no substantial difference in the activity of the catalysts in other reactions regardless of the potassium loading. These studies have shown that the influence of potassium varies depending on the reaction, which highlights differences in the impact of reducibility and importance of other factors in these reactions

Study of the Influence of the Change from Methyl to Isopropyl Substituents in 1-(2,4,6-trialkylphenyl)ethanol on the Point Group Symmetry of the 0-D Hydrogen-Bonded Moiety

The steric hindrance in molecules of 1-(2,4,6-trimethylphenyl)ethanone and 1-(2,4,6-triisopropylphenyl)ethanone were shown to substantially differentiate the options of synthesis of the respective alcohols. The former was obtained with a yield of 12% with a mild reducing agent, i.e., NaBH4, as well as in vapor phase transfer hydrogenation (22% yield at 673 K) over MgO, whereas the latter was not formed at all under those conditions. The only agent that was able to reduce both ketones was LiAlH4. The single crystals of the two alcohols were obtained and their structures were determined. The symmetry of the 0-D hydrogen-bonded networks of molecules in these crystals was analyzed. It was shown that the methyl substituent allows the molecules to form hexameric rings, whereas the isopropyl-substituted molecules formed tetrameric ones. In both cases, there were two types of rings in the cell, but four types of molecules forming tetramers and only three types of molecules in the hexamers. These structures were compared to similar structures formed by other molecules found in the Cambridge Structural Database via hydrogen bonding. Moreover, the single crystal of 1-(2,4,6-triisopropylphenyl)ethanone was obtained to explain if either the hydrogen bonding or the presence of isopropyl groups influences the angles in the molecules

Application of Slow Pyrolysis to Convert Waste Plastics from a Compost-Reject Stream into Py-Char

There is growing recognition that the degradation of plastics in the environment is a serious problem. This study investigated and reported on the feasibility of removing end-of-life plastics from circulating in the environment. The specific example focuses on non-recyclable plastics found in a waste diversion program for compostable materials, known as the Green Bin Program. The purpose of this study was to identify and quantify the types of polymers in this stream, as well as to determine if it could be successfully turned into char without separation of its components. The measurements show that polyethylene (72 wt.%), polypropylene (14 wt.%) and polyethylene terephthalate (12 wt.%) are the main constituents of this stream, with minor contributions from polybutylene adipate terephthalate (PBAT), polyvinyl alcohol (PVA), poly methyl methacrylate (PMMA), polystyrene (PS), Nitrile rubber and Nylon. Samples of the as-received waste containing plastics and fibrous material were subjected to a slow pyrolysis process. The yield of the char product depended on the conditions of the pyrolysis and a strong synergistic effect was noted when both the plastic and fibrous materials were co-pyrolyzed. The study of variable pyrolysis conditions, along with DTA-TGA-MS studies on the mechanism of the char formation, indicate that the positive effect results from enhanced interaction of plastics with air, in the presence of fibrous material, during the initial/pre-treatment step

Application of Slow Pyrolysis to Convert Waste Plastics from a Compost-Reject Stream into Py-Char

There is growing recognition that the degradation of plastics in the environment is a serious problem. This study investigated and reported on the feasibility of removing end-of-life plastics from circulating in the environment. The specific example focuses on non-recyclable plastics found in a waste diversion program for compostable materials, known as the Green Bin Program. The purpose of this study was to identify and quantify the types of polymers in this stream, as well as to determine if it could be successfully turned into char without separation of its components. The measurements show that polyethylene (72 wt.%), polypropylene (14 wt.%) and polyethylene terephthalate (12 wt.%) are the main constituents of this stream, with minor contributions from polybutylene adipate terephthalate (PBAT), polyvinyl alcohol (PVA), poly methyl methacrylate (PMMA), polystyrene (PS), Nitrile rubber and Nylon. Samples of the as-received waste containing plastics and fibrous material were subjected to a slow pyrolysis process. The yield of the char product depended on the conditions of the pyrolysis and a strong synergistic effect was noted when both the plastic and fibrous materials were co-pyrolyzed. The study of variable pyrolysis conditions, along with DTA-TGA-MS studies on the mechanism of the char formation, indicate that the positive effect results from enhanced interaction of plastics with air, in the presence of fibrous material, during the initial/pre-treatment step

Catalytic Transfer Hydrogenation Performance of Magnesium-Doped ZrO₂ Solid Solutions

This is the first study to investigate the activity of a solid solution containing magnesium ions in a zirconia matrix in the catalytic transfer hydrogenation (CTH) of acetophenone with 2-pentanol. The results have shown that magnesium oxide is very highly active in CTH when physically mixed with zirconia. However, the same concentration of Mg2+ ions (Mg:Zr = 3:97) inserted into a zirconia lattice did not yield high activity in CTH. A higher concentration of Mg2+ ions (5%) was also tested in the two types of systems, i.e., a physical mixture of oxides and a solid solution. The increase in the concentration of Mg2+ ions in the physical mixture led to a pronounced increase in the activity of the system, whereas in the case of the solid solution it led to a slight decrease in activity. The impact of the zirconyl salt used in the synthesis was also examined, but showed little effect on the properties and activity of the systems. The study has also shown that the increase of the concentration of magnesium ions caused a decrease in the m-ZrO2 to t-ZrO2 ratio. Nevertheless, the rate of heating had an even bigger effect on this ratio

CO Removal from Hydrogen Stream through Methanation on Ru/C Catalysts Doped with Lanthanum and Barium

The influence of the lanthanum and barium addition on the physicochemical properties and catalytic behavior of the Ru/C catalyst for CO methanation was investigated. The catalyst was doped with La or with La plus Ba. It was found out that there are various ways the additives were applied in the study, thus changing the catalytic performance of the basic material and influencing the susceptibility of the carbon support in relation to undesired methanation. The highest catalytic activity, 23.46 (mmol CO/gC+Ru × h), was achieved for the LaRu/C system, with methane selectivity exceeding 80% over the whole temperature range. Ba addition caused a significant decrease in activity. TG-MS studies revealed that both La and Ba improved the resistance of the carbon support to undesired methanation. Detailed characterization methods, employing XRPD, Raman spectroscopy, CO chemisorption, and SEM-EDX, showed that the catalytic behavior of the studied catalysts was attributed to lanthanum distribution over the Ru/C materials surface and structural changes in the carbon support affecting electron supply to the metallic active phase

Catalytic Activity of High-Surface-Area Amorphous MgO Obtained from Upsalite

The first aim of the research was to synthesize a pure Upsalite, which is an amorphous form of MgCO3, by modifying a procedure described in the literature, so that it would be the precursor of a high-surface, amorphous magnesium oxide. The results indicate that within the studied reaction conditions, the type of alcohol used as the reactant has the most pronounced effect on the yield of reaction. From the two alcohols that led to the highest yield of Upsalite, methanol gave a substantially larger surface area (794 vs. 191 m2 g−1). The optimized synthesis conditions of Upsalite were used to obtain MgO via thermolysis, whose activity in the transfer hydrogenation reaction (THR) from ethanol, 2-propanol and 2-pentanol to various carbonyl compounds was determined. The optimal conditions for the thermolysis were as follows: vacuum, T = 673 K as the final temperature, and a heating rate of 2 deg min−1. The high-surface, amorphous magnesia (SBET = 488 m2 g−1) was found to be a very selective catalyst to 4-t-butylcyclohexanone in THR, which led to a diastereoselectivity of over 94% to the E-isomer of 4-t-butylcyclohexanol for more than 3 h, with conversions of up to 97% with either 2-propanol or 2-pentanol as the hydrogen donor. In the case of acrolein and 2-n-propylacrolein being used as the hydrogen acceptors, the unsaturated alcohol (UOL) was the main product of the reaction, with higher UOL yields noted for ethanol than 2-propanol

Highly Active Large Au Clusters and Even More Active Ag Nanoparticles Supported on Ceria-Zirconia: Impact of Particle Size and Potassium Ion Loading on Activity in Catalytic Transfer Hydrogenation

Although heterogeneous monometallic gold catalysts are commonly more active when the gold particles are smaller, this study shows that the reverse is true in the case of liquid phase catalytic transfer hydrogenation of acetophenone with 2-pentanol. Higher catalytic activity of larger gold particles, i.e., over 30 nm in diameter, than of smaller particles of average 4 nm in size was observed. Moreover, this effect was contradictory to that observed for supported monometallic silver catalysts in which the interaction with the support and hence particle size was shown to cause drastic changes in the activity in this reaction, with the large particles being completely inactive and tiny ones being the most active system studied. In this reaction, the ceria-zirconia solid solutions were used as the supports for the catalysts and both zirconium doped ceria, as well as cerium doped zirconia carriers were tested. The supports themselves exhibited little activity in this reaction. It was shown that the activity of the supports and catalysts depends on the Ce/Zr ratio and potassium content. Both types of catalysts showed excellent selectivity to 1-phenylethanol and conversion of acetophenone, although it was noted that a high loading of potassium carbonate in the gold catalysts propelled undesired reactions, thereby reducing the selectivity to 1-phenylethanol

A Hands-on Guide to the Synthesis of High-Purity and High-Surface-Area Magnesium Oxide

In this study, magnesium nitrate, chloride or sulphate were used in the synthesis of Mg(OH)2, the precursor of MgO. It was found that the counter ion strongly influences the purity of the Mg(OH)2, as well as the specific surface area of the obtained MgO. The latter is also strongly influenced by the calcination temperature. The choice of the precipitating agent can lead to the introduction of K+ or Na+ ions and hence NH3 (aq) is the best choice. A multistep precipitation procedure of Mg(OH)2 was proposed to lower the concentration of typical impurities (Fe, Ni and Mn) found in commercial p.a. purity Mg(NO3)2. The effect of the number of portions of water used for washing of Mg(OH)2 on the purity of the final product has also been investigated in detail. The stages of formation of grains of Mg(OH)2 and their subsequent thermal decomposition was described together with determination of the introduction of new impurities into the material. Large scale (1500 g) preparation of Mg(OH)2 with an improved purity was performed and described. Therefore, this study explains what measures should be taken to obtain pure magnesia catalysts and is a valuable resource for catalytic research in which magnesia is used