Role of support in reforming of CH4 with CO2 over Rh catalysts

The reforming of CH₄ with CO₂ over supported Rh catalysts has been studied over a range of temperatures (550–1000 K). A significant effect of the support on the catalytic activity was observed, where the order was Rh/Al₂O₃>Rh/TiO₂>Rh/SiO₂. The catalytic activity of Rh/SiO₂ was promoted markedly by physical mixing of Rh/SiO₂ with metal oxides such as Al₂O₃, TiO₂, and MgO, indicating a synergetic effect. The role of the metal oxides used as the support and the physical mixture may be ascribed to the promotion in dissociation of CO₂ on the surface of Rh, since the CH₄ + CO₂ reaction is first order in the pressure of CO₂, suggesting that CO₂ dissociation is the rate-determining step. The possible model of the synergetic effect was proposed.     

Selective formation of CH3OH in the photocatalytic reduction of CO2 with H2O on titanium oxides highly dispersed within zeolites and mesoporous molecular sieves

Highly dispersed titanium oxide catalysts have been prepared within zeolite cavities as well as in the zeolite framework and utilized as photocatalysts for the reduction of CO₂ with H₂O to produce CH₄ and CH₃OH at 328 K. In situ photoluminescence, ESR, diffuse reflectance absorption and XAFS investigations indicate that the titanium oxide species are highly dispersed within the zeolite cavities and framework and exist in tetrahedral coordination. The charge transfer excited state of the highly dispersed titanium oxide species play a significant role in the reduction of CO₂ with H₂O with a high selectivity for the formation of CH₃OH, while the catalysts involving the aggregated octahedrally coordinated titanium oxide species show a high selectivity to produce CH₄, being similar to reactions on the powdered TiO₂ catalysts. Ti-mesoporous molecular sieves exhibit high photocatalytic reactivity for the formation of CH₃OH, its reactivity being much higher than the powdered TiO₂ catalysts. The addition of Pt onto the highly dispersed titanium oxide catalysts promotes the charge separation which leads to an increase in the formation of CH₄ in place of CH₃OH formation.     

Fabrication of damascene Cu wirings using solid acidic catalyst

The copper damascene process is one of the most promising technologies for fabricating Cu wirings for electronic devices such as LSIs. In this research, the fabrication of damascene Cu wirings was conducted using solid acidic catalyst. When a Cu-plated wafer, whose oxide is a basic oxide is dipped into a mixture of oxidizing solution and acidic solution, surface atoms are ionized and etched off into the solution. However, because conventional nonelectrolytic etching does not have a reference surface, it is difficult to utilize for planarization. Therefore, a new nonelectrolytic machining method using a cation-exchange fabric instead of an acidic solution was developed. To be more precise, the planarization of a Cu-plated wafer was carried out by rubbing with the cation-exchange fabric in ozone water. Basically, this method exploits chemical reactions so that the physical properties of the workpiece surface are not deteriorated. Furthermore, this method uses no chemicals except for ozone water, which easily dissociates into water and oxygen molecules; thus, this method is a low-cost, environmentally friendly process. In this paper, as a preliminary experiment, the nonelectrolytic etching of a Cu sample using solutions of O₃ and CO₂ was carried out to inspect the dependence of the etching rate on [O₃] and [H⁺]. The results indicate that the etching rate increased as [O₃] and [H⁺] increased. When [H⁺] was high relative to [O₃], a smooth etch-pit-free surface was achieved. Next, nonelectrolytic etching using a cation-exchange fabric was carried out, and properties similar to those in the case of etching using solutions were obtained. Finally, damascene Cu wirings were fabricated using ozone water and a cation-exchange catalyst.     

Revolving Vernier Mechanism Controls Size of Linear Homomultimer

A new kind of the Vernier mechanism that is able to control the size of linear assembly of DNA origami nanostructures is proposed. The mechanism is realized by mechanical design of DNA origami, which consists of a hollow cylinder and a rotatable shaft in it connected through the same scaffold. This nanostructure stacks with each other by the shape complementarity at its top and bottom surfaces of the cylinder, while the number of stacking is limited by twisting angle of the shaft. Experiments have shown that the size distribution of multimeric assembly of the origami depends on the twisting angle of the shaft; the average lengths of the multimer are decamer, hexamer, and tetramer for 0°, 10°, and 20° twist, respectively. In summary, it is possible to affect the number of polymerization by adjusting the precise shape and movability of a molecular structure.     

A decentralized control scheme for orchestrating versatile arm movements in ophiuroid omnidirectional locomotion

Autonomous decentralized control is a key concept for understanding the mechanism underlying the adaptive and versatile behaviour of animals. Although the design methodology of decentralized control based on a dynamical system approach that can impart adaptability by using coupled oscillators has been proposed in previous studies, it cannot reproduce the versatility of animal behaviours comprehensively. Therefore, our objective is to understand behavioural versatility from the perspective of well-coordinated rhythmic and non-rhythmic movements. To this end, we focus on ophiuroids as a simple good model of living organisms that exhibit spontaneous role assignment of rhythmic and non-rhythmic arm movements, and we model such arm movements by using an active rotator model that can describe both oscillatory and excitatory properties. Simulation results show that the spontaneous role assignment of arm movements is successfully realized by using the proposed model, and the simulated locomotion is qualitatively equivalent to the locomotion of real ophiuroids. This fact can potentially facilitate a better understanding of the control mechanism responsible for the orchestration of versatile arm movements in ophiuroid omnidirectional locomotion.     

Doped Helium Crystals Growth and Study

No Heading The new technique for embedding microimpurities into solid helium has been developed. A He crystal was grown in a vertical cylindrical cell placed in the bath of pumped LHe cryostat. The He solid was continuously moved downward by exhaust of helium from the cell bottom and was simultaneously restored from its upper edge by sedimentation of a jet of gas helium mixed with impurity. A guest particle density of 3· 10¹⁹ per cc and stable during an hour doped crystal growth with the rate of 1 mm per 20 s were achieved. The solid Deuterium clusters isolated in solid Helium have been investigated at T = 1.3K and P = 3 MPa by CARS technique. The strong effect of Raman scattering sensitivity to the molecular environment nuclear spin has been found in CARS - the ratio of probabilities for the scattering by para (J=1) and ortho (J=0) deuterium being equal to 1 in a gas is as high as 10,000 in nearly pure o-D₂, whereas it is 50 in common Raman scattering. This effect has been shown to give rise starting from cluster size corresponding to the phonon band onset.PACS numbers: 33.20 Fb; 33.70 Jg: 67.80 Mg     

Repeated temperature modulation epitaxy for p-type doping and light-emitting diode based on ZnO.

Since the successful demonstration of a blue light-emitting diode (LED), potential materials for making short-wavelength LEDs and diode lasers have been attracting increasing interest as the demands for display, illumination and information storage grow. Zinc oxide has substantial advantages including large exciton binding energy, as demonstrated by efficient excitonic lasing on optical excitation. Several groups have postulated the use of p-type ZnO doped with nitrogen, arsenic or phosphorus, and even p-n junctions. However, the choice of dopant and growth technique remains controversial and the reliability of p-type ZnO is still under debate. If ZnO is ever to produce long-lasting and robust devices, the quality of epitaxial layers has to be improved as has been the protocol in other compound semiconductors. Here we report high-quality undoped films with electron mobility exceeding that in the bulk. We have used a new technique to fabricate p-type ZnO reproducibly. Violet electroluminescence from homostructural p-i-n junctions is demonstrated at room-temperature.