A study on the preparation of supported metal oxide catalysts using JRC-reference catalysts. I. Preparation of a molybdena–alumina catalyst. Part 4. Preparation parameters and impact index

The effects of the volume and pH of the impregnation solution and of the calcination conditions were examined on the physicochemical and catalytic properties of a 13 wt% MoO₃/Al₂O₃ extrudate catalyst. The Al₂O₃ support and drying procedures (static conditions without flowing air) were fixed in the preparations. In the present series of catalysts, the amount of crystalline MoO₃ was marginally small. It was found that the dispersion of Mo oxide species increased as the volume of the impregnation solution increased, gradually approaching a maximum value. The increase in pH (2–8) of the impregnation solution was found to reduce the dispersion of Mo oxide species. The Mo dispersion increased slightly for the impregnation catalysts as the calcination temperature increased (673–873 K), whereas it decreased for the equilibrium adsorption catalysts. The effects of the calcination atmosphere (with or without flowing air, or with flowing humid air) were very small on the dispersion of Mo oxide species under the present preparation conditions. On the other hand, the methanol oxidation activity of MoO₃/Al₂O₃ was sensitive to the preparation parameters examined here. It was demonstrated by means of EPMA and XPS that a considerable migration of Mo took place during the calcination.

In the present study on the preparation of a 13 wt% MoO₃/Al₂O₃ catalyst, an impact index is proposed to measure the magnitude of the effects of the respective parameter(s) on the physicochemical and catalytic properties. With the Mo dispersion, the effects of the preparation parameter decreased in the order, surface area of the support >> drying process > volume of the impregnation solution > pH, calcination temperature and atmosphere. The size of the impact index for the dispersion of Mo sulfide species is 70–75% of that for the Mo oxide species. The HDS activity of the catalyst was less affected by the preparation parameters than the Mo sulfide dispersion. The preparation parameters affected the segregation of Mo on the outer surface of extrudates in a decreasing order: drying process > volume of the impregnation solution > pH, calcination conditions. It was found that the oxidation of methanol was affected most intensely by the drying procedures. The volume of the impregnation solution, calcination conditions and pH of the impregnation solution also strongly affected the oxidation activity. The impact index suggests that the sensitivity to the preparation variables of the physicochemical and catalytic properties of MoO₃/Al₂O₃ decreases in the order, methanol oxidation activity > surface Mo segregation > Mo oxide dispersion > Mo sulfide dispersion > HDS activity.     

Photoalignment and Surface‐Relief‐Grating Formation are Efficiently Combined in Low‐Molecular‐Weight Halogen‐Bonded Complexes

It is demonstrated that halogen bonding can be used to construct low‐molecular‐weight supramolecular complexes with unique light‐responsive properties. In particular, halogen bonding drives the formation of a photoresponsive liquid‐crystalline complex between a non‐mesogenic halogen bond‐donor molecule incorporating an azo group, and a non‐mesogenic alkoxystilbazole moiety, acting as a halogen bond‐acceptor. Upon irradiation with polarized light, the complex exhibits a high degree of photoinduced anisotropy (order parameter of molecular alignment > 0.5). Moreover, efficient photoinduced surface‐relief‐grating (SRG) formation occurs upon irradiation with a light interference pattern, with a surface‐modulation depth 2.4 times the initial film thickness. This is the first report on a halogen‐bonded photoresponsive low‐molecular‐weight complex, which furthermore combines a high degree of photoalignment and extremely efficient SRG formation in a unique way. This study highlights the potential of halogen bonding as a new tool for the rational design of high‐performance photoresponsive suprastructures.     

Fabrication of Ni compound nanocrystal/nanocarbon composites by cooling of chloride-based fluxes

Unique Ni compound nanocrystals were successfully grown on carbon nanotubes (CNTs) by cooling a mixed chloride flux. Cup-stacked CNTs (CSCNTs) were used as the nanocarbon materials because of their structural features. The grown nanocrystals had a nanosheet structure, which was densely assembled and had a ribbon-like morphology. Therefore, the nanocrystal/CSCNT composites were expected to have a highly active surface area for the catalyst composites. The selected area electron diffraction pattern and the related radial intensity profiles indicated that the grown nanocrystals were Ni(OH)2. When the pristine CSCNTs were used as a starting material, the formation efficiency of the nanocrystal/CSCNT composites decreased because the pristine CSCNTs were not dispersed in the KCl-LiCl flux. Therefore, functionalization of the CSCNTs was carried out with VUV light irradiation. The dispersibility of the VUV light-treated CSCNTs increased in the KCl-LiCl flux in comparison with the pristine CSCNTs because oxygen-containing functional groups, such as -COOH and -CO, were introduced onto the surfaces of the CSCNTs.     

Evaluation on plastic deformation property of copper nano-film by nano-scale cantilever specimen

We investigate the elasto-plastic deformation properties of a 20-nm-thick copper (Cu) thin film. A nano-scale cantilever specimen is fabricated from multilayer thin films, where the Cu thin film is sandwiched between a silicon nitride layer and a silicon substrate. During bending, the load, P, and displacement, d, are carefully monitored using an electron microscope, and a distinct non-linearity is observed. The plastic constitutive equation of the Cu thin film, which is assumed to obey a power hardening law (σ = Rεⁿ (σ > σ_y)), is inversely derived by finite element method fitting the experimental results. The residual stress in each layer is experimentally examined, and the effect is included in the inverse analysis. We obtain σ = 3316ε^0.29 [MPa] and a yield stress of 765 MPa for the Cu film. The yield stress is about 10 times higher than that of the bulk, and the exponent is also larger. Moreover, inverse analysis based on the bending experiment data, without considering the residual stress, gives a good approximation of the plastic law. This is because the plastic deformation preferentially takes place at the top and bottom surfaces, where the residual stress is relieved during fabrication of the specimen.     

Numerical Flow Simulation in Turbine Mode of Counter-Rotating Type Pumping Unit to Cooperate with Wind Turbine

This serial research has proposed the hybrid power system combined the wind power unit with the counter-rotating type pump-turbine unit, to provide the constant output for the grid system, even at the suddenly fluctuating/turbulent wind circumstance. In this paper, the tandem impellers prepared for the counter-rotating type pumping unit were operated at the turbine mode, and the performances and the flow conditions were investigated numerically with accompanying the experimental results. Even though providing the pumping unit for the turbine mode, the maximum hydraulic efficiency is close to one of the counter-rotating type hydroelectric unit designed exclusively for the turbine mode. Besides, the runners/impellers of the unit work evidently so as to coincide the angular momentum change through the front runners/impellers with that through the rear runners/impellers, namely to take the axial flow at not only the inlet but also the outlet, without the guide vanes. From these results, it can be concluded that this type unit is effective to work at not only the pumping but also the turbine modes.     

Fabrication of highly crystalline NbOx nanotube/cup-stacked CNT nanocomposites

Carbon nanotubes (CNTs) are promising catalyst supports for fuel cell applications. Metal oxide/CNT nanocomposites are also being studied for dye-sensitized solar-cell, photocatalyst, and sensor applications. The fabrication of nanocomposites consisting of highly crystalline NbOx nanotubes and cup-stacked carbon nanotubes (CSCNTs) is reported herein. The CSCNTs were selected for the carbon materials because of their distinctive structure. The CSCNTs were photochemically treated with vacuum ultraviolet light, which increased the amount of oxygen-containing functional groups therein. NbOx nanotubes with no defects were successfully prepared with the chemical treatment of highly crystalline, layered, flux-grown K4Nb6O17 crystals. First, K4Nb6O17 crystals were grown from a KCl flux at a holding temperature of 800 degrees C. Next, NbOx nanosheets were prepared from the layered K4Nb6O17 crystals via a two-step exfoliation process, which consists of proton exchange in an acid solution and intercalation of the tetrabutylammonium ions. The NbOx nanosheets were rolled up into nanotubes with diameters of about 20 nm and lengths of 100-500 nm on the surfaces of the CSCNTs; thus, unique and complex NbOx/CSCNT nanocomposites were successfully fabricated.     

Homology-Based Interactions between Small RNAs and Their Targets Control Dominance Hierarchy of Male Determinant Alleles of Self-Incompatibility in Arabidopsis lyrata

Self-incompatibility (SI) is conserved among members of the Brassicaceae plant family. This trait is controlled epigenetically by the dominance hierarchy of the male determinant alleles. We previously demonstrated that a single small RNA (sRNA) gene is sufficient to control the linear dominance hierarchy in Brassica rapa and proposed a model in which a homology-based interaction between sRNAs and target sites controls the complicated dominance hierarchy of male SI determinants. In Arabidopsis halleri, male dominance hierarchy is reported to have arisen from multiple networks of sRNA target gains and losses. Despite these findings, it remains unknown whether the molecular mechanism underlying the dominance hierarchy is conserved among Brassicaceae. Here, we identified sRNAs and their target sites that can explain the linear dominance hierarchy of Arabidopsis lyrata, a species closely related to A. halleri. We tested the model that we established in Brassica to explain the linear dominance hierarchy in A. lyrata. Our results suggest that the dominance hierarchy of A. lyrata is also controlled by a homology-based interaction between sRNAs and their targets.     

Application of energy capacitor system to wind power generation

In this paper, it is reported that energy capacitor system (ECS), which combines power electronic devices and electric double‐layer capacitor, can significantly decrease voltage and power fluctuations of grid‐connected fixed‐speed wind generator. The proper selection of wind farm output power reference is still a problem for smoothing the wind farm output power. This paper proposes exponential moving average to generate the reference output power of a grid‐connected wind farm. The objective of the control system is to follow the line power reference by absorbing or providing real power to or from the ECS. Moreover, the necessary reactive power can also be supplied to keep the wind farm terminal voltage at the desired reference level. Real wind speed data were used in the simulation analyses, which validate the effectiveness of the proposed control strategy. Simulation results clearly show that our proposed ECS can be suitable for wind power application. Copyright © 2007 John Wiley & Sons, Ltd.     

Precipitation control of calcium phosphate on pure magnesium by anodization

Calcium phosphate precipitated on pure magnesium from artificial plasma (modified Hanks’ solution) was varied by anodization and autoclaving, aiming the control of corrosion rate of bioabsorbable magnesium. Rough and smooth anodized film was formed depending on anodizing voltage in 1 N NaOH. The amount of calcium phosphate precipitated on the porous film was 2-3 times larger than that on the smooth film. The Ca/P ratio on the porous film was slightly higher than that on the smooth film. The autoclaving did not significantly influence the morphology of anodized film; however, the precipitation of calcium phosphate was restricted. No significant local corrosion occurred after the immersion in modified Hanks’ solution. It is demonstrated that the precipitation of calcium phosphate on magnesium can be controlled by anodization and autoclaving.