Catalytic selective reduction of NO with propylene over Cu-Al2O3 catalysts: influence of catalyst preparation method

NO reduction to N₂ by C₃H₆ was investigated and compared over Cu-Al₂O₃ catalysts prepared by four different methods, namely, the conventional impregnation, co-precipitation, evaporation of a mixed aqueous solution, and xerogel methods. It was found that the catalyst preparation method as well as the Cu content exerts a significant influence on catalyst activity. For the catalysts prepared by the first three preparation methods, with the increase of Cu content from 5 to 15 wt%, the maximum NO reduction conversion decreased slightly, but the temperature for the maximum NO reduction also decreased. For the xerogel Cu-Al₂O₃, there was a significant decrease in NO reduction conversion with the increase of Cu content from 5 to 10 wt%. In the absence of water vapour, the Cu-Al₂O₃ catalyst prepared by the impregnation method exhibited the highest activity toward NO reduction. The purity of alumina support was found to be a crucial factor to the activity of the Cu-Al₂O₃ catalyst prepared by impregnation. In the presence of water vapour, a substantial decrease in NO conversion was observed for the Cu-Al₂O₃ catalysts prepared by the first three methods, especially for the impregnated Cu-Al₂O₃ catalyst. In contrast, the presence of water vapour showed only a minor influence on the xerogel 5 wt% Cu-Al₂O₃ and it showed the highest activity for NO reduction in the presence of 20% water vapour. The xerogel 5 wt% Cu-Al₂O₃ catalyst was also found to be less affected by a 5 wt% sulfate deposition than the Cu-Al₂O₃ catalysts prepared by other methods.     

Numerical and experimental analysis of a counter-rotating type horizontal-axis tidal turbine

In order to exploit renewable energies form tidal currents, a unique counter-rotating type horizontal-axis tidal turbine was proposed in this paper. Although a counter-rotating type horizontal-axis wind turbine can be taken as a reference in designing the proposed counterrotating tidal turbine, there are some different characteristics such as the effects of the free surface and the occurrence of cavitation. The unique tidal turbine in this paper was preliminarily designed on the basis of the in-house wind turbine, and then CFD analysis and experimental test were carried out to evaluate its performance. For the extreme conditions where severe flow separation and vortex exist, the comparison of the power coefficients generated by the turbine between the CFD predictions and the experimental data shows not so good. However, good agreement has been obtained for the comfortable blade pitch setting angles and over a range of tip speed ratios, which provides an evidence of validation of CFD analysis. Such results give sufficient confidence that the CFD model set up here is suitable for the further works.     

Synthetic caged DAG-lactones for photochemically controlled activation of protein kinase C

Switching on kinases: Synthetic caged DAG-lactones have been developed and showed decreases of two orders of magnitude, relative to the corresponding parent compounds, in their binding affinities towards PKC. The caged compounds had no effect on the translocation of PKC until after photoactivation. This approach is a potentially powerful tool for probing the PKC signaling cascade.     

Preparation of polybenzimidazole/functionalized carbon nanotube nanocomposite films for use as protective coatings

Functionalized multi‐walled carbon nanotubes (MWCNTs) via microwave‐induced polymerization modification route, and polybenzimidazole (PBI) nanocomposite films containing 0.1‐5 wt% functionalized MWCNTs were successfully synthesized. The functionalized MWCNTs were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and X‐ray photoelectron spectroscopy (XPS). The results verify that the polymer was successfully grafted to the MWCNTs with a polymer layer that was several nanometers thick. The TGA results showed that the quantity of the attached polymer reached approximately 9.4 wt%. The mechanical properties of the nanocomposite films were measured by tensile test and dynamic mechanical analysis (DMA). The tensile test results indicated that the Young's modulus increased by about 43.9% at 2 wt% CNT loading, and further modulus growth was observed at higher filler loading. The DMA studies indicated that the nanocomposite films had a higher storage modulus than pure PBI film in the temperature range of 30‐300°C, and the storage modulus was maintained above 0.82 GPa. Simulation results confirmed that the PBI nanocomposite films had desirable mechanical properties for use as a protective coating. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers.     

Uptake of heavy metal ions from aqueous solution using Mg–Al layered double hydroxides intercalated with citrate, malate, and tartrate

Mg–Al layered double hydroxide (Mg–Al LDH) was modified with organic acid anions using a coprecipitation technique, and the uptake of heavy metal ions from aqueous solution by the Mg–Al LDH was studied. Citrate·Mg–Al LDH, malate·Mg–Al LDH, or tartrate·Mg–Al LDH, which had citrate³⁻ (C₆H₅O₇³⁻), malate²⁻ (C₄H₄O₅²⁻), or tartrate²⁻ (C₄H₄O₆²⁻) anions intercalated in the interlayer, was prepared by dropwise addition of a mixed aqueous solution of Mg(NO₃)₂ and Al(NO₃)₃ to a citrate, malate, or tartrate solution at a constant pH of 10.5. These Mg–Al LDHs were found to take up Cu²⁺ and Cd²⁺ rapidly from an aqueous solution at a constant pH of 5.0. This capacity was mainly attributable to the formation of the citrate–metal, malate–metal, and tartrate–metal complexes in the interlayers of the Mg–Al LDHs. The uptake of Cu²⁺ increased in the order malate·Mg–Al LDH < tartrate·Mg–Al LDH < citrate·Mg–Al LDH. The uptake of Cd²⁺ increased in the order malate·Mg–Al LDH < tartrate·Mg–Al LDH = citrate·Mg–Al LDH. These differences in Cu²⁺ and Cd²⁺ uptake were attributable to differences in the stabilities of the citrate–metal, malate–metal, and tartrate–metal complexes. These results indicate that citrate³⁻, malate²⁻, and tartrate²⁻ were adequately active as chelating agents in the interlayers of Mg–Al LDHs.     

Electronic and magnetic properties of acid-adsorbed nanoporous activated carbon fibers

Nanoporous activated carbon fibers (ACFs) feature 3D disordered networks of nanographite domains that consist of stacks of 3-4 nanographene sheets each. At the peripheries of the nanographene sheets, the localized spins of a nonbonding edge state are created. The magnetic properties of the edge-state spins in ACFs are investigated in relation to the interaction with acid molecules adsorbed in the nanopores. HCl molecules condensed physisorptively in the nanopores mechanically compress the nanographite domains, resulting in the reduction of the magnetic moments of the edge-state spin in the form of a magnetic switching effect. HNO₃ molecules, which have significant oxidation ability, are subjected to charge transfer from the nanographite domains. This induces a two-step reduction in the edge-state spin concentration, wherein the first and second steps are related to the charge transfer with the nanographene sheets that directly face the nanopores and that with the nanographene sheets in the interior of the nanographite domains, respectively. In diluted HNO₃, the blockade by water molecules prevents the interaction of the HNO₃ molecules with the interior nanographene sheets, allowing for charge transfer only with the graphene sheets that directly face the nanopores; this results in a single-step change in the spin concentration.     

Oxidation of all‐cis‐7,10,13,16,19‐docosapentaenoic acid ethyl ester. Hydroperoxide distribution and volatile characterization

The isomeric hydroperoxide distribution and the composition of volatiles generated by oxidation of all‐cis‐7,10,13,16,19‐docosapentaenoic acid ethyl ester (DPA Et) were determined. DPA Et was prepared by using seal blubber oils as raw material and purified by urea complexation and reverse‐phase high‐performance liquid chromatography (HPLC). The DPA Et of over 96% purity thus obtained was dissolved in methanol and subsequently divided into two portions. One portion was added with methylene blue and exposed to a tungsten bulb light at 5 °C for photosensitized oxidation. The other portion was added with 2,2'‐azobis (2,4‐dimethylvaleronitrile) as an azo‐radical initiator and kept in the dark at room temperature for autoxidation. Positional isomers of hydroperoxides generated by autoxidation or photosensitized oxidation of DPA Et were separated by normal‐phase HPLC and detected by a fluorescence detection system as well as UV absorption. The peak components were identified by gas chromatography‐mass spectrometry (GC‐MS). Eight isomeric hydroperoxides, including certain amounts of 7‐, 10‐, 11‐, 13‐, 14‐, 16‐, 17‐, and 20‐hydroperoxy docosapentaenoate, were generated by autoxidation of DPA Et. The photosensitized oxidation of DPA Et yielded not only the above eight hydroperoxide isomers but also two additional isomeric hydroperoxides, 8‐ and 19‐hydroperoxy docosapentaenoate, which are characteristic hydroperoxide isomers generated by singlet oxygen‐mediated oxidation. Volatiles formed by autoxidation of DPA Et at 50 °C were collected and analyzed by solid‐phase micro‐extraction and GC/GC‐MS. A number of aldehydes, ketones, alcohols, acids, furans and hydrocarbons were identified. The formation mechanisms of certain volatiles are discussed.     

Influence of NH4Cl Powder Addition for Fabrication of Aluminum Nitride Coating in Reactive Atmospheric Plasma Spray Process

Reactive plasma spray is the key to fabricating aluminum nitride (AlN) thermally sprayed coatings. It was possible to fabricate AlN/Al composite coatings using atmospheric plasma spray process through plasma nitriding of Al powders (Al 30 ??m). The nitriding reaction and the AlN content could be improved by controlling the spray distance and the feedstock powder particle size. Increasing the spray distance and/or using smaller particle size of Al powders improved the in-flight nitriding reaction. However, it was difficult to fabricate thick and dense AlN coatings with an increase in the spray distance and/or when using fine particles. Thus, the coatings thickness was suppressed because of the complete nitriding of some particles (formation of AlN particles) during flight, which prevents the particle deposition. Furthermore, the excessive vaporization of Al fine particles (due to increased particle temperature) decreased the deposition efficiency. To fabricate thick AlN coatings in the reactive plasma spray process, improving the nitriding reaction of the large Al particles at short spray distance is required to decrease the vaporization of Al particles during flight. This study investigated the influence of adding ammonium chloride (NH₄Cl) powders on the nitriding process of large Al powders and on the microstructure of the fabricated coatings. It was possible to fabricate thick AlN coatings at 100 mm spray distance with small addition of NH₄Cl powders to the Al feedstock powders (30 ??m). Addition of NH₄Cl to the starting Al powders promoted the formation of AlN through changing the reaction path to vapor-phase nitridation chlorination-nitridation sequences as confirmed by the thermodynamic analysis of possible intermediate reactions. This changes the nitriding reaction to a mild way, so it is more controlled with no explosive mode and with relatively low heating rates. Thus, NH₄Cl acts as a catalyst, nitrogen source, and diluent agent. Furthermore, the evolved gases from the sublimation or decomposition of NH₄Cl can prevent the Al particles coalescing after melting.     

Reactive Atmospheric Plasma Spraying of AlN Coatings: Influence of Aluminum Feedstock Particle Size

Feedstock powder characteristics (size distribution, morphology, shape, specific mass, and injection rate) are considered to be one of the key factors in controlling plasma-sprayed coatings microstructure and properties. The influence of feedstock powder characteristics to control the reaction and coatings microstructure in reactive plasma spraying process (RPS) is still unclear. This study, investigated the influence of feedstock particle size in RPS of aluminum nitride (AlN) coatings, through plasma nitriding of aluminum (Al) feedstock powders. It was possible to fabricate AlN-based coatings through plasma nitriding of all kinds of Al powders in atmospheric plasma spray (APS) process. The nitriding ratio was improved with decreasing the particle size of feedstock powder, due to improving the nitriding reaction during flight. However, decreasing the particle size of feedstock powder suppressed the coatings thickness. Due to the loss of the powder during the injection, the excessive vaporization of fine Al particles and the completing nitriding reaction of some fine Al particles during flight. The feedstock particle size directly affects on the nitriding, melting, flowability, and the vaporization behaviors of Al powders during spraying. It concluded that using smaller particle size powders is useful for improving the nitriding ratio and not suitable for fabrication thick AlN coatings in reactive plasma spray process. To fabricate thick AlN coatings through RPS, enhancing the nitriding reaction of Al powders with large particle size during spraying is required.