New catalytic functions of Pd–Zn, Pd–Ga, Pd–In, Pt–Zn, Pt–Ga and Pt–In alloys in the conversions of methanol

Pd and Pt supported on ZnO, Ga₂O₃ and In₂O₃ exhibit high catalytic performance for the steam reforming of methanol, CH₃OH+H₂OCO₂+3HH₂, and the dehydrogenation of methanol to HCOOCH₃, 2CH₃OHHCOOCH₃+2HH₂. Combined results with temperature-programmed reduction (TPR) and XRD method revealed that Pd–Zn, Pd–Ga, Pd–In, Pt–Zn, Pt–Ga and Pt–In alloys were produced upon reduction. Over the catalysts having the alloy phase, the reactions proceeded selectively, whereas the catalysts having metallic phase exhibited poor selectivities.     

Study on chemical structures of poly (tetrafluoroethylene-co-perfluoroalkylvinylether) by soft-EB irradiation in solid and molten state

Poly (tetrafluoroethylene-co-perfluoroalkylvinylether) (PFA) was irradiated by soft electron beam (soft-EB) under nitrogen gas atmosphere in solid-state and its molten state, respectively. The changes of thermal property and chemical structures of irradiated PFA in solid-state and molten state were studied by differential scanning calorimetric analysis (DSC) and solid-state ¹⁹F magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. By DSC analysis, the melting temperature shifted to lower temperatures, and crystallinity decreased with increasing soft-EB dose. By solid-state ¹⁹F MAS NMR spectroscopy, the new signals was observed and the detected new signals in irradiated PFA at 315 °C and at 30 °C were due to the tertiary carbon group with branching site (Y-type crosslinking site), perfluoro-propylene site and chain end methylene groups, respectively.Moreover, the molar ratio of perfluoroalkylvinylether (FAVE) structure to -CF₂- units decreased with increasing dose.     

Effects of magnetic field and hydrostatic pressure on martensitic transformation

Effects of magnetic field and hydrostatic pressure on martensitic transformations in some ferrous and nonferrous alloys have been studied. The studies clarified the effects of magnetic field and hydrostatic pressure on martensitic transformation start temperature, magnetoelastic martensitic transformation, morphology of martensites and transformation kinetics of athermal and isothermal transformations. That is, transformation start temperatures of all the ferrous alloys examined increase with increasing magnetic field, but those of non-ferrous, such as Ti-Ni and Cu-Al-Ni shape memory alloys, are not affected. On the other hand, transformation start temperature decreases with increasing hydrostatic pressure in some ferrous alloys, but increases in Cu-Al-Ni alloys. The magnetic field and hydrostatic pressure dependences of the martensitic start temperature are in good agreement with those calculated by the equations proposed by our group. In the work on the Fe-Ni-Co-Ti alloy, we found that magnetoelastic martensitic transformation appear. In addition, several martensite plates grow nearly parallel to the direction of applied magnetic field in the specimen of an Fe-Ni alloy single crystal. Moreover, we found that the isothermal process in an Fe-Ni-Mn alloy changes to the athermal one under magnetic field and the athermal process changes to the isothermal one under hydrostatic pressure. Based on the facts, a phenomenological theory is constructed, which unifies the two transformation processes.     

Kinetics of oxidation of cuprous chloride by oxygen in aqueous hydrochloric acid solutions

The rates of absorption of oxygen into aqueous cuprous chloride solutions containing hydrochloric acid were measured at 15, 25 and 35°C using a baffled agitated vessel operated batchwise and the experimental results were analyzed with the chemical absorption theory. The reaction between oxygen and cuprous chloride was found to be second order, i.e. first order with respect to oxygen and CuCl₂^? ion which is the actual reactive species in aqueous cuprous chloride solutions containing hydrochloric acid. The reaction rate constants were calculated and correlated as a function of temperature.     

Photoinduced Magnetization with a High Curie Temperature and a Large Coercive Field in a Co‐W Bimetallic Assembly

The crystal structure, magnetic properties, and temperature‐ and photoinduced phase transition of [{Co^II(4‐methylpyridine)(pyrimidine)}₂{Co^II(H₂O)₂}{W^V(CN)₈}₂]·4H₂O are described. In this compound, a temperature‐induced phase transition from the Co^II (S = 3/2)‐NC‐W^V(S = 1/2) [high‐temperature (HT)] phase to the Co^III(S = 0)‐NC‐W^IV(S = 0) [low temperature (LT)] phase is observed due to a charge‐transfer‐induced spin transition. When the LT phase is irradiated with 785 nm light, ferromagnetism with a high Curie temperature (T_C) of 48 K and a gigantic magnetic coercive field (H_c) of 27 000 Oe are observed. These T_C and H_c values are the highest in photoinduced magnetization systems. The LT phase is optically converted to the photoinduced phase, which has a similar valence state as the HT phase due to the optically induced charge‐transfer‐induced spin transition.     

New catalytic technologies in Japan

Recent trends in R&D of catalytic technology in Japan (cleaner and more efficient production, environmental catalysts, and recycling processes) are overviewed and examples of recent achievements are listed. Examples are then described as zeolite-catalyzed organic reactions recently commercialized and expected to be commercialized: hydration of cyclohexene, synthesis of pyridine derivatives and gas-phase Beckmann rearrangement of cyclohexanone oxime. Finally, as an example of environmental catalysts, the NO_x storage–reduction type three-way automobile catalyst, is introduced.     

Effective synthesis of ethanol from CO2 on polyfunctional composite catalysts

Synthesis of ethanol by hydrogenation of carbon dioxide has been investigated by developing the novel composite catalysts. The three different kinds of elementary reaction functions for ethanol synthesis were undertaken. The catalytic functions are partial reduction of CO₂ to CO, C–C bond formation, and –OH group insertion. For this purpose, supported Rh catalyst, Fe-based modified Fisher–Tropsch catalyst, and Cu-based modified methanol synthesis catalyst were combined by different ways. As a result, high space–time yields of ethanol as high as 0.8–0.9 kg/l h were obtained.     

Photosensitized hydrogen evolution from water using a single-walled carbon nanotube/fullerodendron/SiO2 coaxial nanohybrid

A coaxial nanohybrid consisting of a single-walled carbon nanotube (SWCNT), fullerodendron, and SiO(2) shows high-efficiency light-driven hydrogen evolution from water. Upon visible light irradiation, SWCNT/fullerodendron/SiO(2) coaxial nanohybrid shows hydrogen evolution activity in the presence of methyl viologen (MV(2+)), benzyldihydronicotinamide (BNAH), and a colloidal polyvinyl alcohol(PVA)-Pt.     

Oxygen Potential Analysis to Evaluate Irradiation Behavior in MOX and MA-Bearing MOX Fuels

Oxygen potentials of oxide nuclear fuels are important thermodynamic data in development of nuclear fuel technologies. Minor actinide bearing MOX （mixed oxide） fuels have been developed as sodium cooled fast reactor fuels. Content of Am which is one of the minor actinide elements causes oxygen potentialto increase. The effects of the oxygen potential increase on the irradiation behavior were evaluated. Profiles of temperature and O/M （oxygen-to-metal） ratio in the pellets were evaluated to better understand the irradiation behavior. From these data, local oxygen potential in the radial direction of the pellets was calculated, and was compared with free energy of compounds composed of fission products. Based on this comparison, it was concluded that Cs2MoO4 was likely formed at pellet periphery of （U07Pu03）O1.98 and （U0.66Pu03Amoo16Npo.016）Ol.976 The extent of cladding tube inner surface oxidation was predicted by using the calculated oxygen potential. No significant difference between irradiation behaviors of （Uo.7Puo3）O2_x and （U0.66PUo 3Amo.016Npo.016）O2.x pellets was confirmed.