High activity, templated mesoporous SO4/ZrO2/HMS catalysts with controlled acid site density for α-pinene isomerisation

Highly active mesoporous SO4/ZrO2/HMS (hexagonal mesoroporous silica) solid acid catalysts with tuneable sulphated zirconia (SZ) content have been prepared for the liquid phase isomerisation of α-pinene. The mesoporous HMS framework is preserved during the grafting process as evidenced by the X-ray diffraction (XRD) and porosimetry with all SO4/ZrO2/HMS materials possessing average pore-diameters ∼20 Å. XRD confirms the presence of a stabilized tetragonal phase of nanoparticulate ZrO2, with no evidence for zirconia phase separation or the formation of discrete crystallites, consistent with a uniform and highly dispersed SZ coating. The activity towards α-pinene isomerisation scales linearly with Zr loading, while the specific activities are an order of magnitude greater than attainable by conventional methodologies (∼1 versus 0.08 mol h−1 g Zr−1).

Structure-reactivity correlations in MgAl hydrotalcite catalysts for biodiesel synthesis

A series of [Mg(1−x)Alx(OH)2]x+(CO3)x/n2− hydrotalcite materials with compositions over the range x = 0.25–0.55 have been synthesised using an alkali-free coprecipitation route. All materials exhibit XRD patterns characteristic of the hydrotalcite phase with a steady lattice expansion observed with increasing Mg content. XPS measurements reveal a decrease in both the Al and Mg photoelectron binding energies with Mg incorporation which correlates with the increased intra-layer electron density. All materials are effective catalysts for the liquid phase transesterification of glyceryl tributyrate with methanol for biodiesel production. The rate increases steadily with Mg content, with the Mg rich Mg2.93Al catalyst an order of magnitude more active than MgO, with pure Al2O3 being completely inert. The rate of reaction also correlates with intralayer electron density which can be associated with increased basicity.© 2005 Elsevier B.V. All rights reserved.

Structure-reactivity correlations in the selective aerobic oxidation of cinnamyl alcohol:in situ XAFS

The structural evolution of a Pd/C catalyst during the liquid phase selective aerobic oxidation of cinnamyl alcohol has been followed by in situ XAFS and XPS. The fresh catalyst comprised highly dispersed, heavily oxidised Pd particles. Cinnamyl alcohol oxidation resulted in the rapid reduction of surface palladium oxide and a small degree of concomitant particle growth. These structural changes coincided with a large drop in catalytic activity. Prereduced Pd/C exhibited a significantly lower initial oxidation rate demonstrating the importance of surface metal oxide in effecting catalytic oxidation. Use of a Pd black model system confirmed that the oxide→metal transformation was the cause, and not result, of catalyst deactivation.

Selectivity control in Pt-catalyzed cinnamaldehyde hydrogenation

Chemoselectivity is a cornerstone of catalysis, permitting the targeted modification of specific functional groups within complex starting materials. Here we elucidate key structural and electronic factors controlling the liquid phase hydrogenation of cinnamaldehyde and related benzylic aldehydes over Pt nanoparticles. Mechanistic insight from kinetic mapping reveals cinnamaldehyde hydrogenation is structure-insensitive over metallic platinum, proceeding with a common Turnover Frequency independent of precursor, particle size or support architecture. In contrast, selectivity to the desired cinnamyl alcohol product is highly structure sensitive, with large nanoparticles and high hydrogen pressures favoring C=O over C=C hydrogenation, attributed to molecular surface crowding and suppression of sterically-demanding adsorption modes. In situ vibrational spectroscopies highlight the role of support polarity in enhancing C=O hydrogenation (through cinnamaldehyde reorientation), a general phenomenon extending to alkyl-substituted benzaldehydes. Tuning nanoparticle size and support polarity affords a flexible means to control the chemoselective hydrogenation of aromatic aldehydes.

Solid biofuel production by mechanical pre-treatment of brewers' spent grain

The brewing industry produces large amounts of by-products and wastes like brewers' spent grain (BSG). In Germany, each year approximately 2.1 million tonnes of BSG are generated. During the last years conventional routes of BSG utilization face a remarkable change, such as the decline in the demand as animal feed. Due to its high content of organic matter energetic utilization may create an additional economic value for breweries. Furthermore, in the recent past breweries tend to shift their energy supply towards more sustainable concepts. Although, a decent number of research projects were carried out already, still no mature strategy is available. However, one possible solution can be the mechanical pretreatment of BSG. This step allows optimized energy utilization by the fractionation of BSG. Due to the transfer of digestible components, such as protein, to the liquid phase, the solid phase will largely consist of combustible components. That represents an opportunity to produce a solid biofuel with lower fuelnitrogen content compared to only thermal dried BSG. Therefore, two main purposes for the mechanical pre-treatment were determined, (1) to reduce the moisture content to at least 60 % (w/w) and (2) to diminish the protein content of the solid phase by 30 %. Moreover, the combustion trials should demonstrate whether stable processes and flue gas emissions within the legal limits in Germany are feasible. The results of the mechanical pre-treatment trials showed that a decrease of the moisture and protein content has been achieved. With regard to the combustion trials inconsistent outcomes were found. On the one hand a stable combustion was realized. On the other hand the legal emission levels of NOx (500 mgm -3) and dust (50 mgm-3) could not be kept during all trials. The further research steps will focus on the optimization of the air/fuel ratio by reducing the primary and secondary air conditions. Copyright © 2014,AIDIC Servizi S.r.l.

Highly selective hydrogenation of furfural over supported Pt nanoparticles under mild conditions

The selective liquid phase hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on SiO2, ZnO, γ-Al2O3, CeO2 is reported under extremely mild conditions. Ambient hydrogen pressure, and temperatures as low as 50 °C are shown sufficient to drive furfural hydrogenation with high conversion and >99% selectivity to furfuryl alcohol. Strong support and solvent dependencies are observed, with methanol and n-butanol proving excellent solvents for promoting high furfuryl alcohol yields over uniformly dispersed 4 nm Pt nanoparticles over MgO, CeO2 and γ-Al2O3. In contrast, non-polar solvents conferred poor furfural conversion, while ethanol favored acetal by-product formation. Furfural selective hydrogenation can be tuned through controlling the oxide support, reaction solvent and temperature.

Self-assembled SnO2 micro- and nanosphere-based gas sensor thick films from an alkoxide-derived high purity aqueous colloid precursor

Tin oxide is considered to be one of the most promising semiconductor oxide materials for use as a gas sensor. However, a simple route for the controllable build-up of nanostructured, sufficiently pure and hierarchical SnO2 structures for gas sensor applications is still a challenge. In the current work, an aqueous SnO2 nanoparticulate precursor sol, which is free of organic contaminants and sorbed ions and is fully stable over time, was prepared in a highly reproducible manner from an alkoxide Sn(OR)4 just by mixing it with a large excess of pure neutral water. The precursor is formed as a separate liquid phase. The structure and purity of the precursor is revealed using XRD, SAXS, EXAFS, HRTEM imaging, FTIR, and XRF analysis. An unconventional approach for the estimation of the particle size based on the quantification of the Sn-Sn contacts in the structure was developed using EXAFS spectroscopy and verified using HRTEM. To construct sensors with a hierarchical 3D structure, we employed an unusual emulsification technique not involving any additives or surfactants, using simply the extraction of the liquid phase, water, with the help of dry butanol under ambient conditions. The originally generated crystalline but yet highly reactive nanoparticles form relatively uniform spheres through self-assembly and solidify instantly. The spheres floating in butanol were left to deposit on the surface of quartz plates bearing sputtered gold electrodes, producing ready-for-use gas sensors in the form of ca. 50 μm thick sphere-based-films. The films were dried for 24 h and calcined at 300°C in air before use. The gas sensitivity of the structures was tested in the temperature range of 150-400°C. The materials showed a very quickly emerging and reversible (20-30 times) increase in electrical conductivity as a response to exposure to air containing 100 ppm of H2 or CO and short (10 s) recovery times when the gas flow was stopped.

Estudo de um compósito Nb-15%pCu obtidos por moagem de alta energia e sinterizados por fase líquida

There is great difficulty in forming a composite refractory metal niobium with copper. This is due to the fact that Nb-Cu system is almost mutually immiscible and may be neglected solubility between them. These properties hinder or prevent obtaining homogeneous and high-density structures, conventionally prepared. This study aims to analyze the use of high-energy milling process (MAE) to implement these natural difficulties, with regard to the densification of the sintered bodies. The MAE and the press were used in the preparation of powders, to obtain a fine and homogeneous distribution of the grain size. Four loads Nb and Cu powders containing 15% by weight of Cu were then milled for MAE in a planetary type ball mill under various milling times and speeds. The results obtained by MAE were analyzed by scanning electron microscopy (SEM), according to the parameters of time and grinding speed. The samples were compacted under pressure of 200 MPa, were then sintered in liquid phase in a vacuum furnace at temperatures of 1100 ° C / 60 min and 1200 ° C / 60 min. Then it was used to characterize diffraction of X-rays to identify the phases. The microstructures of the sintered samples were observed and evaluated using scanning electron microscopy (SEM). Vickers Microhardness tests were performed, obtaining higher values for the sintered bodies in the largest of the post milling times and the larger grinding speeds. It was found that the liquid phase sintering of the samples that were processed by MAE produced at the end of a homogeneous and densified structure in 77,4% relative to the value of the theoretical density of the composite

Efeito da moagem de alta energia na densificação e microestrutura do compósito AI2O3-Cu

The Cu-Al2O3 composite ceramic combines the phase of alumina, which is extremely hard and durable, yet very brittle, to metallic copper phase high ductility and high fracture toughness. These characteristics make this material a strong candidate for use as a cutting tool. Al2O3-Cu composite powders nanocrystalline and high homogeneity can be produced by high energy milling, as well as dense and better mechanical structures can be obtained by liquid phase sintering. This work investigates the effect of high-energy milling the dispersion phase Al2O3, Cu, and the influence of the content of Cu in the formation of Cu-Al2O3 composite particles. A planetary mill Pulverisatte 7 high energy was used to perform the experiments grinding. Al2O3 powder and Cu in the proportion of 5, 10 and 15% by weight of Cu were placed in a container for grinding with balls of hard metal and ethyl alcohol. A mass ratio of balls to powder of 1:5 was used. All powders were milled to 100 hours, and powder samples were collected after 2, 10, 20, 50 and 70 hours of grinding. Composite powders with compact cylindrical shape of 8 mm diameter were pressed and sintered in uniaxial matrix resistive furnace to 1200, 1300 to 1350 °C for 60 minutes under an atmosphere of argon and hydrogen. The heating rate used was 10°C/min. The powders and structures of the sintered bodies were characterized by XRD, SEM and EDS. Analysis TG, DSC and particle size were also used to characterize the milled powders, as well as dilatometry was used to observe the contraction of the sintered bodies. The density of the green and sintered bodies was measured using the geometric method (mass / volume). Vickers microhardness with a load of 500 g for 10 s were performed on sintered structures. The Cu-Al2O3 composite with 5% copper density reached 61% of theoretical density and a hardness of 129 HV when sintered at 1300 ° C for 1h. In contrast, lower densities (59 and 51% of the theoretical density) and hardness (110 HV and 105) were achieved when the copper content increases to 10 and 15%.

Estudo de duas pseudoligas de Nb-Cu obtidas pela rota da metalurgia do pó

The Nb-Cu pseudoalloys present themselves as potential substitutes for the alloys from a well known system and already commercially applied, as the W-Cu alloys, used in applications such as heat sinks, electrical contacts and coils for the generation of high magnetic fields. Because it is an immiscible system, where there is mutual insolubility and low wettability of the liquid Cu on the Nb surface, the processing route used in this work was the Powder Metallurgy. Two Nb alloys were used, with additions of 10% and 20% in weight of Cu, and times of 20, 30 and 40 hours for the high energy milling of the starting powders. The milling evolution of the powders is presented through the characterization techniques, such as the LASER diffraction for particle size, XRD, SEM, EDS, DSC, dilatometry, TEM and chemical analysis. After the milling, portions of the loads were submitted to the annealing heat treatment. The process used for the samples consolidation was the hot pressing, which has been applied both on some milled powders samples, as on the annealed powders. Subsequent heat treatments were performed in the samples at temperatures of 1000ºC (solid phase) and 1100ºC (in the Cu liquid phase). All sets of consolidated samples, and also the two sets of the heat treated, were analyzed by XRD, SEM, EDS, density and Vickers microhardness. Moreover, other Nb powder samples with 10% and 20% in weight of Cu obtained by simple mechanical mixing, were consolidated, thermally treated and characterized with the same techniques applied to the others, and the results were compared among themselves. Despite the difficulty of consolidation and densification of the two pseudoalloys of the Nb-Cu system of this study, on the route that passes through the HEM, samples were obtained with densities around 90% of the theoretical density. And, on the processing route of which were only mixed, the values reached up to 97%. Therefore, in this work are also emphasized the processes that made possible these results.

Avaliação do desempenho da paligorsquita modificada e do carvão da pirólise do lodo de esgoto no processo de degradação fotocatalítica do fenol

The uncontrolled disposal of wastewaters containing phenolic compounds by the industry has caused irreversible damage to the environment. Because of this, it is now mandatory to develop new methods to treat these effluents before they are disposed of. One of the most promising and low cost approaches is the degradation of phenolic compounds via photocatalysis. This work, in particular, has as the main goal, the customization of a bench scale photoreactor and the preparation of catalysts via utilization of char originated from the fast pyrolysis of sewage sludge. The experiments were carried out at constant temperature (50°C) under oxygen (410, 515, 650 and 750 ml min-1). The reaction took place in the liquid phase (3.4 liters), where the catalyst concentration was 1g L-1 and the initial concentration of phenol was 500 mg L-1 and the reaction time was set to 3 hours. A 400 W lamp was adapted to the reactor. The flow of oxygen was optimized to 650 ml min-1. The pH of the liquid and the nature of the catalyst (acidified and calcined palygorskite, palygorskite impregnated with 3.8% Fe and the pyrolysis char) were investigated. The catalytic materials were characterized by XRD, XRF, and BET. In the process of photocatalytic degradation of phenol, the results showed that the pH has a significant influence on the phenol conversion, with best results for pH equal to 5.5. The phenol conversion ranged from 51.78% for the char sewage sludge to 58.02% (for palygorskite acidified calcined). Liquid samples analyzed by liquid chromatography and the following compounds were identified: hydroquinone, catechol and maleic acid. A mechanism of the reaction was proposed, whereas the phenol is transformed into the homogeneous phase and the others react on the catalyst surface. For the latter, the Langmuir-Hinshelwood model was applied, whose mass balances led to a system of differential equations and these were solved using numerical methods in order to get estimates for the kinetic and adsorption parameters. The model was adjusted satisfactorily to the experimental results. From the proposed mechanism and the operating conditions used in this study, the most favored step, regardless of the catalyst, was the acid group (originated from quinone compounds), being transformed into CO2 and water, whose rate constant k4 presented value of 0.578 mol L-1 min-1 for acidified calcined palygorskite, 0.472 mol L-1 min-1 for Fe2O3/palygorskite and 1.276 mol L-1 min-1 for the sludge to char, the latter being the best catalyst for mineralization of acid to CO2 and water. The quinones were adsorbed to the acidic sites of the calcined palygorskite and Fe2O3/palygorskite whose adsorption constants were similar (~ 4.45 L mol-1) and higher than that of the sewage sludge char (3.77 L mol-1).

Avaliação do desempenho da paligorsquita modificada e do carvão da pirólise do lodo de esgoto no processo de degradação fotocatalítica do fenol

The uncontrolled disposal of wastewaters containing phenolic compounds by the industry has caused irreversible damage to the environment. Because of this, it is now mandatory to develop new methods to treat these effluents before they are disposed of. One of the most promising and low cost approaches is the degradation of phenolic compounds via photocatalysis. This work, in particular, has as the main goal, the customization of a bench scale photoreactor and the preparation of catalysts via utilization of char originated from the fast pyrolysis of sewage sludge. The experiments were carried out at constant temperature (50°C) under oxygen (410, 515, 650 and 750 ml min-1). The reaction took place in the liquid phase (3.4 liters), where the catalyst concentration was 1g L-1 and the initial concentration of phenol was 500 mg L-1 and the reaction time was set to 3 hours. A 400 W lamp was adapted to the reactor. The flow of oxygen was optimized to 650 ml min-1. The pH of the liquid and the nature of the catalyst (acidified and calcined palygorskite, palygorskite impregnated with 3.8% Fe and the pyrolysis char) were investigated. The catalytic materials were characterized by XRD, XRF, and BET. In the process of photocatalytic degradation of phenol, the results showed that the pH has a significant influence on the phenol conversion, with best results for pH equal to 5.5. The phenol conversion ranged from 51.78% for the char sewage sludge to 58.02% (for palygorskite acidified calcined). Liquid samples analyzed by liquid chromatography and the following compounds were identified: hydroquinone, catechol and maleic acid. A mechanism of the reaction was proposed, whereas the phenol is transformed into the homogeneous phase and the others react on the catalyst surface. For the latter, the Langmuir-Hinshelwood model was applied, whose mass balances led to a system of differential equations and these were solved using numerical methods in order to get estimates for the kinetic and adsorption parameters. The model was adjusted satisfactorily to the experimental results. From the proposed mechanism and the operating conditions used in this study, the most favored step, regardless of the catalyst, was the acid group (originated from quinone compounds), being transformed into CO2 and water, whose rate constant k4 presented value of 0.578 mol L-1 min-1 for acidified calcined palygorskite, 0.472 mol L-1 min-1 for Fe2O3/palygorskite and 1.276 mol L-1 min-1 for the sludge to char, the latter being the best catalyst for mineralization of acid to CO2 and water. The quinones were adsorbed to the acidic sites of the calcined palygorskite and Fe2O3/palygorskite whose adsorption constants were similar (~ 4.45 L mol-1) and higher than that of the sewage sludge char (3.77 L mol-1).

Efeito da adição de WC e Co na sinterização e propriedades mecânicas da alumina

Composites based on alumina (Al2O3), tungsten carbide (WC) and cobalt (Co) exhibit specific properties such as low density, high oxidation resistance, high melting point and high chemical inertia. That composite shows to be a promising material for application in various fields of engineering. In this work, the mechanical properties of the composite (Al2O3 – WC – Co), particularly density and hardness, were evaluated according to the effects of the variables of powder processing parameters, green compact and sintered. Powder composites with the composition of 80 wt% Al2O3, 18 wt% WC and 2 wt% Co were processed by high energy ball milling in a planetary mill for 50 hours as well as mixed by manual mixing in a glass vessel with the same proportion. Samples were collected (2, 10, 20, 30, 40 and 50 hours) during the milling process. Then, the powders were compacted in a cylindrical die with 5 mm in diameter in a uniaxial press with pressures of 200 and 400 MPa. The sintering was in two stages: first, the solid phase sintering was performed at 1126 and 1300 °C for 1 hour with a heating rate of 10 °C/min in a resistive furnace under argon atmosphere for green samples compacted in 200 and 400 MPa; the second sintering was performed on dilatometer in solid phase at 1300 °C for green sample compacted in 200 MPa, another sintering also was performed on dilatometer, this time in liquid phase at 1550 °C for green samples compacted in 200 and 400 MPa, with the same parameters used in resistive furnace. The raw materials were characterized by X – ray diffraction (XRD), X – ray fluorescence (XRF), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and laser particlemeter. The sintered samples were subjected to microhardness testing. The results showed that high energy milling achieved to the objectives regarding the particle size and the dispersion of composite phases. However, the hardness did not achieve to significant results, this is an indication that the composite has low fracture toughness.

Efeito da adição de WC e Co na sinterização e propriedades mecânicas da alumina

Composites based on alumina (Al2O3), tungsten carbide (WC) and cobalt (Co) exhibit specific properties such as low density, high oxidation resistance, high melting point and high chemical inertia. That composite shows to be a promising material for application in various fields of engineering. In this work, the mechanical properties of the composite (Al2O3 – WC – Co), particularly density and hardness, were evaluated according to the effects of the variables of powder processing parameters, green compact and sintered. Powder composites with the composition of 80 wt% Al2O3, 18 wt% WC and 2 wt% Co were processed by high energy ball milling in a planetary mill for 50 hours as well as mixed by manual mixing in a glass vessel with the same proportion. Samples were collected (2, 10, 20, 30, 40 and 50 hours) during the milling process. Then, the powders were compacted in a cylindrical die with 5 mm in diameter in a uniaxial press with pressures of 200 and 400 MPa. The sintering was in two stages: first, the solid phase sintering was performed at 1126 and 1300 °C for 1 hour with a heating rate of 10 °C/min in a resistive furnace under argon atmosphere for green samples compacted in 200 and 400 MPa; the second sintering was performed on dilatometer in solid phase at 1300 °C for green sample compacted in 200 MPa, another sintering also was performed on dilatometer, this time in liquid phase at 1550 °C for green samples compacted in 200 and 400 MPa, with the same parameters used in resistive furnace. The raw materials were characterized by X – ray diffraction (XRD), X – ray fluorescence (XRF), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and laser particlemeter. The sintered samples were subjected to microhardness testing. The results showed that high energy milling achieved to the objectives regarding the particle size and the dispersion of composite phases. However, the hardness did not achieve to significant results, this is an indication that the composite has low fracture toughness.

MOVPE growth and characterization of Al(Ga)N and InAlN/AlGaN quantum wells for UV LED applications

The study of III-nitride materials (InN, GaN and AlN) gained huge research momentum after breakthroughs in the production light emitting diodes (LEDs) and laser diodes (LDs) over the past two decades. Last year, the Nobel Prize in Physics was awarded jointly to Isamu Akasaki, Hiroshi Amano and Shuji Nakamura for inventing a new energy efficient and environmental friendly light source: blue light-emitting diode (LED) from III-nitride semiconductors in the early 1990s. Nowadays, III-nitride materials not only play an increasingly important role in the lighting technology, but also become prospective candidates in other areas, for example, the high frequency (RF) high electron mobility transistor (HEMT) and photovoltaics. These devices require the growth of high quality III-nitride films, which can be prepared using metal organic vapour phase epitaxy (MOVPE). The main aim of my thesis is to study and develop the growth of III-nitride films, including AlN, u-AlGaN, Si-doped AlGaN, and InAlN, serving as sample wafers for fabrication of ultraviolet (UV) LEDs, in order to replace the conventional bulky, expensive and environmentally harmful mercury lamp as new UV light sources. For application to UV LEDs, reducing the threading dislocation density (TDD) in AlN epilayers on sapphire substrates is a key parameter for achieving high-efficiency AlGaNbased UV emitters. In Chapter 4, after careful and systematic optimisation， a working set of conditions, the screw and edge type dislocation density in the AlN were reduced to around 2.2×108 cm-2 and 1.3×109 cm-2 , respectively, using an optimized three-step process, as estimated by TEM. An atomically smooth surface with an RMS roughness of around 0.3 nm achieved over 5×5 µm 2 AFM scale. Furthermore, the motion of the steps in a one dimension model has been proposed to describe surface morphology evolution, especially the step bunching feature found under non-optimal conditions. In Chapter 5, control of alloy composition and the maintenance of compositional uniformity across a growing epilayer surface were demonstrated for the development of u-AlGaN epilayers. Optimized conditions (i.e. a high growth temperature of 1245 °C) produced uniform and smooth film with a low RMS roughness of around 2 nm achieved in 20×20 µm 2 AFM scan. The dopant that is most commonly used to obtain n-type conductivity in AlxGa1-xN is Si. However, the incorporation of Si has been found to increase the strain relaxation and promote unintentional incorporation of other impurities (O and C) during Si-doped AlGaN growth. In Chapter 6, reducing edge-type TDs is observed to be an effective appoach to improve the electric and optical properties of Si-doped AlGaN epilayers. In addition, the maximum electron concentration of 1.3×1019 cm-3 and 6.4×1018 cm-3 were achieved in Si-doped Al0.48Ga0.52N and Al0.6Ga0.4N epilayers as measured using Hall effect. Finally, in Chapter 7, studies on the growth of InAlN/AlGaN multiple quantum well (MQW) structures were performed, and exposing InAlN QW to a higher temperature during the ramp to the growth temperature of AlGaN barrier (around 1100 °C) will suffer a significant indium (In) desorption. To overcome this issue, quasi-two-tempeature (Q2T) technique was applied to protect InAlN QW. After optimization, an intense UV emission from MQWs has been observed in the UV spectral range from 320 to 350 nm measured by room temperature photoluminescence.