CeO2–ZrO2 Solid Solution Catalyst for Selective Synthesis of Dimethyl Carbonate from Methanol and Carbon Dioxide

CeO₂–ZrO₂ solid solution catalysts are very effective for the selective synthesis of dimethyl carbonate from methanol and CO₂. The activity was much dependent on the calcination temperature. The higher the calcination temperature, the higher the activity of the catalyst for DMC formation, though the BET surface area is lower on the catalyst calcined at higher temperature.     

Structure and mechanical properties of multi‐hollowed fibers produced by CO2 laser irradiated neck drawing

Multi‐hollowed fibers with a hollowness ratio of over 20% were successfully produced using a neck‐drawing technique accompanied by CO₂ laser irradiation on unoriented and amorphous polytrimethylene terephthalate (PTT) fibers with diameters of approximately 104 µm. The structure and mechanical properties of the multi‐hollowed fibers were characterized using scanning electron microscopy, wide angle X‐ray diffraction (WAXD), birefringence measurements, and tensile tests. Crystal orientation factors in the direction normal to the (010) and (002) planes, which were obtained from WAXD patterns, were lower in comparison to values obtained in previous studies on fibers that did not feature these hollows [9] because of the development of these internal hollows. The PTT fibers in this study also displayed high toughness, about 465 MPa (3.5 cN/dtex) strength and about 40% elongation, and had excellent elastic recovery (>95%) after 10 stretch cycles. POLYM. ENG. SCI., 56:609–616, 2016. © 2015 Society of Plastics Engineers     

Development and evaluation of a palm-sized optical PM2.5 sensor

A new palm-sized optical PM_2.5 sensor has been developed and its performance evaluated. The PM_2.5 mass concentration was calculated from the distribution of light scattering intensity by considering the relationship between scattering intensity and particle size. The results of laboratory tests suggested that the sensor can detect particles with diameters as small as ～0.3 µm and can measure PM_2.5mass concentrations as high as ～600 µg/m³. Year-round ambient observations were conducted at four urban and suburban sites in Fukuoka, Kadoma, Kasugai, and Tokyo, Japan. Daily averaged PM_2.5 mass concentration data from our sensors were in good agreement with corresponding data from the collocated standard instrument at the Kadoma site, with slopes of 1.07–1.16 and correlation coefficients (R) of 0.90–0.91, and with those of the nearest observatories of the Ministry of the Environment of Japan, at 1.7–4.1 km away from our observation sites, with slopes of 0.97–1.23 and R of 0.89–0.95. Slightly greater slopes were observed in winter than in summer, except at Tokyo, which was possibly due to the photochemical formation of relatively small secondary particles. Under high relative humidity conditions (>70%), the sensor has a tendency to overestimate the PM_2.5 mass concentrations compared to those measured by the standard instruments, except at Fukuoka, which is probably due to the hygroscopic growth of particles. This study demonstrates that the sensor can provide reasonable PM_2.5 mass concentration data in urban and suburban environments and is applicable to studies on the environmental and health effects of PM_2.5.

Copyright © 2018 American Association for Aerosol Research     

Hydrodechlorination of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) over supported ruthenium and other noble metal catalysts

The hydrodechlorination of CCl₂F–CClF₂ (CFC-113) was studied using silica- and activated carbon-supported Ru, Rh, Pd, and Pt catalysts. The activity of the catalysts changed with time-on-stream. Ru was most stable among the four noble metals and gave a simple product distribution yielding CClF=CF₂ (CFC-1113) and CHClF–CClF₂ (HCFC-123a) as main products. Over silica-supported Ru, CFC-1113 yield decreased gradually with time-on-stream but HCFC-123a yield did not change throughout the reaction, suggesting that these products were formed on different sites of Ru. XRD studies and temperature-programmed reduction of the spent catalyst revealed that the deactivation was caused by halogen-containing carbonaceous species accumulated on the Ru surface during the reaction. The carbonaceous species seemed to be formed on the active site for CFC-1113 formation. Because CFC-1113 selectivity was higher over the catalyst having higher Ru dispersion, it was assumed that the hydrodechlorination of CFC-113 is structure-sensitive and CFC-1113 formation is promoted by Ru having highly unsaturated coordination sphere.     

Hydrogenation of nitro compounds with supported platinum catalyst in supercritical carbon dioxide

Hydrogenation of a series of substituted nitro compounds such as 2-,3-,4-nitroanisole, 2-,3-,4-nitrotoluene, 2,4-dinitrobenzene and 2,4-dinitrotoluene has been studied in supercritical carbon dioxide, scCO₂ (two phases), and ethanol (three phases) with a 5 wt.% carbon supported platinum catalyst. The solubility of these compounds in scCO₂ has also been examined in the presence and absence of hydrogen. The solubility of those nitro compounds increases with increasing CO₂ pressure but decreases with the presence of hydrogen. The solubility is in the order of nitrotoluene > nitroanisole > dinitrotoluene, dinitrobenzene. Although the total conversion obtained with hydrogenation in scCO₂ is similar to that in ethanol, the selectivity to amino products is higher in the former reaction medium, indicating that scCO₂ is an ideal medium for the production of amino compounds with hydrogenation of nitro substrates using conventional supported metal catalysts.     

Effect of temperature on the stereoselectivity of phospholipase D toward glycerol in the transphosphatidylation of phosphatidylcholine to phosphatidylglycerol

In this study, the effect of temperature on the stereoselectivity of phospholipase D (PLD) toward the two primary hydroxyl groups of glycerol in the transphosphatidylation reaction of phosphatidylcholine to phosphatidylglycerol (PtdGro) was investigated. For this purpose, PLD from bacteria (Streptomyces septatus TH-2, S. halstedii subsp. scabies K6, and Actinomadura sp.) and cabbage were tested. At the reaction temperatures employed (0–60°C), the proportions of the two PtdGro diastereomers, namely, 1,2-dioleoyl-sn-glycero-3-phospho-3′-sn-glycerol (R,R configuration) and 1,2-dioleoyl-sn-glycero-3-phosphol-1′-sn-glycerol (R,S configuration), which were produced with PLD from Streptomyces TH-2 and Actinomadura sp., changed gradually from 50% R,R and 50% R,S at 50–60°C to 70% R,R and 30% R,S at O°C. These alterations suggested that the stereoselectivity of the bacterial PLD toward the two primary hydroxyl groups of prochiral glycerol was significantly influenced by reaction temperature. PLD from Streptomyces K6 showed relatively little effect of temperature on stereoselectivity, giving 65–69% R,R in the temperature range of 60–10°C examined. The plots of In ([R,R]/[R,S]) vs. 1/T gave good linear fits for these three bacterial PLD. No temperature effect was observed for cabbage PLD, which gave an almost equimolar mixture of the R,R and R,S diastereomers in the range from 0 to 40°C. The temperature-dependent change in enantiomeric selectivity of the bacterial PLD promises potentially profitable commercial exploitation.     

Synthesis of zirconium diboride platelets from mechanically activated ZrCl4 and B powder mixture

ZrB₂ platelets were prepared by mechanochemical processing a zirconium (IV) chloride–boron mixture with subsequent annealing from 800 °C to 1200 °C. The phases present were identified by X-ray diffraction. The size and morphology of the synthesized ZrB₂ powders were characterized by scanning electron and transmission electron microscopy. At 800 °C, ZrO₂ was detected in absence of ZrB₂. At or above 1000 °C, ZrCl₄–B converted to ZrB₂. Moreover, at 1200 °C, ZrCl₄–B completely converted to ZrB₂ without trace quantities of residual ZrO₂. The synthesized ZrB₂ consisted of platelets with a diameter of 0.1–2.1 μm and a thickness of 40–200 nm.     

Measurement of self-diffusion coefficients in Li ionic conductors by using the short-lived radiotracer of 8Li

For the effective use of short-lived radioactive beams, soon to be available at the Tokai Radioactive Ion Accelerator Complex, the authors have developed a radiotracer method for diffusion studies in solids. The experimental test was performed by the measurement of the diffusion coefficients of Li in a sample of the compound βLiAl using an α-emitting radiotracer of ⁸Li (T_1/2=0.84 s). It was found that the time-dependent yields of the α particles from the diffusing ⁸Li that was initially implanted in the sample could be used as a measure of the diffusivity of the tracer in a nondestructive way. The method was applied to measure the self-diffusion coefficients of Li in βLiGa, and for investigating how the Li diffusion in the Li ionic conductors is affected by the concentration of atomic defects (i.e., the existence of the atomic vacancies of Li and the defects in Ga sites that are replaced by Li).     

Ab initio study on plane defects in zirconium–hydrogen solid solution and zirconium hydride

Hydrogen embrittlement of zirconium alloys is one of the main causes of the mechanical degradation of the fuel cladding in light water reactors, and has therefore been extensively studied. Although various conjectures have been proposed as the origin of such embrittlement, it is not known which one plays the most important role: the brittle nature of the hydride, micro-crack nucleation by interaction of hydride precipitates with dislocations or void nucleation at the interface between hydride precipitates and zirconium matrix. The purpose of the present study was to elucidate the origin of the embrittlement by investigating the fracture properties of the hydride. We have evaluated the surface energy γ_S and unstable stacking energy γ_US of Zr–H systems by using ab initio calculations. The ductile/brittle behavior of the hydride is discussed based on the difference between γ_S and γ_US among the hydride, pure zirconium and hydrogen solid solution. For the solid solution at a H/Zr ratio less than 0.5 we obtained a monotonous decrease by 15–34% and 50–100% in γ_S and γ_US, respectively, from those in pure zirconium, indicating a reduction in both brittleness and ductility. Thus, hydrogen-induced embrittlement of the hcp Zr matrix was not confirmed. On the other hand, for the hydride we obtained a 25% smaller γ_S and a 200–300% larger γ_US than those in pure zirconium. This indicates that zirconium hydride has an extremely brittle nature due to the synergistic effect of a small γ_S, implying easy generation of a fracture surface, and large γ_US, implying a difficulty in dislocation motion, compared with pure zirconium. Furthermore, Rice’s ductile/brittle parameter D was 1.4 in the δ-hydride, indicating that it undergoes brittle fracture more easily than iridium, known as an extremely brittle material. These results seem sufficient to attribute hydrogen embrittlement of zirconium alloys substantially to the brittle nature of the hydride.     

Oxygen Uptake and Release Mechanism of Lithium Manganese Ferrite in the Low Temperature Range of 573–773 K

Oxygen uptake and release of (Li,Mn) ferrite [LMF; (Li_0.60Mn_1.20Fe_1.20)_1−δO₄; δ= 0.007 to 0.033] was investigated concerning the relations between redox reactions of ferrite and cation migration. Mössbauer spectroscopy and X-ray diffractometry showed that some of the Li⁺ and Fe³⁺ ions migrated from the A sites to the B sites of the spinel-type structure and Mn⁴⁺ ions migrated from the B sites to the A sites during oxygen uptake at 573 K. The cation-deficient LMF formed by the oxygen uptake released oxygen molecules in He gas only at 660 K. The cation migration during the oxygen release was in the opposite direction of the movement during oxygen uptake at 573 K.