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61.
The NMR spectra of olefinic protons in the four representative conjugated fatty acid methyl esters, methylcis-9,trans-11-octadecadienoate, methyltrans-9,trans-11-octadecadienoate, methyl α eleostearate, and methyl β eleostearate, were studied. The chemical shift of each olefinic
proton in these compounds was determined by considering their intramolecular environment. Coupling constants were also obtained
as the results of spectral analysis. 相似文献
62.
Fate of the chlorine and fluorine in a sub-bituminous coal during pyrolysis and gasification 总被引:1,自引:0,他引:1
The fate of the chlorine and fluorine present in a sub-bituminous coal from Indonesia during pyrolysis and gasification has been studied with fixed and entrained bed reactors. The rate profile for HCl evolved in the temperature programmed pyrolysis exhibits the main and shoulder peaks at 480 and 600 °C, respectively. Model experiments and subsequent Cl 2p XPS measurements show that HCl reacts with metal impurities and carbon active sites at 500 °C to be retained as inorganic and organic chlorine forms, from which HCl evolves again at elevated temperatures. It is suggested that the HCl observed in the coal pyrolysis may originate from the above-mentioned chlorine functionalities formed by secondary reactions involving the nascent char. In the CO2 gasification of the 900 °C char at 1000 °C and 2.5 MPa, any measurable amounts of HCl and HF could not be detected even at a high conversion of 75 wt% (daf), suggesting the accumulation of these halogens in the residual char. When the coal is injected into an O2-blown, entrained bed gasifier at 1200-1400 °C under 2.6 MPa, the partial oxidation proceeds to a larger extent at a higher O2/coal ratio, whereas the chlorine and fluorine are enriched in the remaining char, and the extent of the enrichment at the latter stage of gasification is larger with the fluorine. The XPS measurements of the chars reveal the presence of the broad F 1 s peak, which can cover a wide range of binding energies attributable to inorganic and organic fluorine. The halogen enrichment during gasification is discussed in terms of secondary reactions of HCl and HF with char. 相似文献
63.
Selective nucleation and deposition of diamonds were achieved on an SiO2-patterned Si substrate. The substrate was pre-treated with an electric field in plasma to introduce diamond nuclei. This treatment did not affect the SiO2 area. Consequently, diamonds grew only on the area where Si was exposed under the conventional conditions of diamond growth. The maximum nucleation density on the area of SiO2was about 5 × 107 cm−2. The ratio of the selectivity was 2 × 102 or higher. This process will be useful and very promising for manufacturing diamond electronic devices. 相似文献
64.
Masahiro Tajima Miki Niwa Yasushi Fujii Yutaka Koinuma Reiji Aizawa Satoshi Kushiyama Satoru Kobayashi Koichi Mizuno Hideo Ohuˆchi 《Applied catalysis. B, Environmental》1997,12(4):1418
The decomposition of chlorofluorocarbons (CFCs) in the presence of water was examined over a variety of solid acid catalysts. The TiO2ZrO2 catalyst was found to have the highest activity and longest life among the catalysts examined. The activity of the TiO2ZrO2 catalysts depended upon the content of TiO2. At the contents of TiO2 from 58 to 90 mole%, the TiO2ZrO2 catalysts exhibited high activity, and these catalysts were proven to contain TiZrO4 crystal. From the study of the XRD peak intensity of the TiZrO4 crystal, it was highest on the TZ-58 which contained 58 mole% of TiO2, and decreased with increasing the content of TiO2. Furthermore, the conversion of CFC113 measured at 673 K was highest at TZ-58, and decreased gradually with increasing TiO2 content. Therefore, the TiZrO4 crystal influences the activity of decomposition of CFC113. However, the TiO2ZrO2 catalyst was gradually deactivated during the reaction due to the elimination of titanium atoms. A good relationship was found between the activity on TiO2ZrO2 catalyst and bond energy of CCl in the compounds of chlorofluorocarbons and hydrochlorocarbons, suggesting that the rate controlling step was the cleavage of CCl bond. 相似文献
65.
X-ray photoelectron spectroscopy was used to investigate the effect of the composition and thickness of surface film on the electrocatalytic properties for chlorine gas evolution on amorphous Pd-Ti-P alloy in NaCl solution. The amount of charge for gas evolution exhibited a wavy change with an increase in polarization potential. The gas evolution became active with an increase in palladium content of the surface film and slowed down with increases of titanium and phosphorus contents of the film. However, despite the fact that the formation of surface film consisting mainly of titanium as a cation in the potential region higher than 1.6 V (sce), the catalytic activity for gas evolution increased, suggesting the change in the gas evolution mechanism in the higher potential region. 相似文献
66.
The catalytic dehydro-aromatization reaction over Mo/HZSM-5 catalyst was drastically stabilized by the co-addition of 5.4%
H2 and 1.8% H2O to methane feed at 750 °C, 0.3 MPa and methane space velocity of 3000 mL g−1 h−1, suppressing the coke formation effectively, compared with single hydrogen or steam addition. 相似文献
67.
N. Kumagai A. Kawashima K. Asami K. Hashimoto 《Journal of Applied Electrochemistry》1986,16(4):565-574
The anodic characteristics of a variety of amorphous palladium-base alloys were examined with a view to their use for the production of sodium hypochlorite by electrolysis of dilute sodium chloride solutions at ambient temperature. The corrosion resistance of palladium-metalloid alloys was obtained by alloying with platinum group metals and/or valve metals. Among these alloys, rhodium-containing alloys showed high electrocatalytic activities for chlorine evolution. Surface activation treatment was, however, necessary to obtain sufficiently high activities for chlorine evolution at low overpotentials. Surface-activated amorphous alloys possessed considerably higher current efficiency for chlorine evolution in comparison with currently used anodes. 相似文献
68.
A solid oxide fuel cell constructed from Ni-SDC anode and LSGM electrolyte was applied to the partial oxidation of methane to syngas (CO+H2) at 700-800 °C with the merits of co-generation of electricity and controllable O2 supply. It was found that the co-generated syngas at H2/CO ratio of 1.4-2.0 varied with applied current densities, CH4 flow rates and operating temperatures. The cell voltage at 100 mA cm−2 and 800 °C was 0.90 V, i.e. about 90 mW cm−2 power density could be obtained. The cell operating at 50 mA cm−2 for 24 h almost showed no degradation of the cell performance. The observed carbon deposition seemed mainly taking place by CH4 cracking reaction. 相似文献
69.
A correlation of the catalytic activity for anodic chlorine evolution of platinum group metals to the nature of the surface film formed during chlorine evolution in a sodium chloride solution was studied by X-ray photoelectron spectroscopy. The change in the surface film with increasing potential was found on platinum, including an increase in the cationic valence. This seemed responsible for the decrease in the activity for chlorine evolution on platinum in the high potential region. Increasing potential did not result in the appreciable increase in the cationic valence in the surface film on the other platinum group metals. Replacement of hydroxyl ions in the surface film by chloride ions became easier in the order of rhodium, iridium and palladium, and the activity for anodic chlorine evolution increased in this order due possibly to an increase in the amount of chloride ions in the film which seemed to be one of the reactants in the rate determining electrochemical desorption of adsorbed chlorine atom. Chlorine molecules adsorbed on the surface film were also found. It was assumed that the activity for anodic chlorine evolution might be low when the metal surface was covered by a large amount of molecular chlorine which was the reaction product. 相似文献
70.
Momoji Kubo Tsuguo Kubota Changho Jung Minako Ando Satoshi Sakahara Kenji Yajima Kotaro Seki Rodion Belosludov Akira Endou Seiichi Takami Akira Miyamoto 《Catalysis Today》2004,89(4):479-493
Recently, we introduced a concept of combinatorial chemistry to computational chemistry and proposed a new method called “combinatorial computational chemistry”, which enables us to perform a theoretical high-throughput screening of catalysts. In the present paper, we reviewed our recent application of our combinatorial computational chemistry approach to the design of new catalysts for high-quality transportation fuels. By using our combinatorial computational chemistry techniques, we succeeded to predict new catalysts for methanol synthesis and Fischer–Tropsch synthesis. Moreover, we have succeeded in the development of chemical reaction dynamics simulator based on our original tight-binding quantum chemical molecular dynamics method. This program realizes more than 5000 times acceleration compared to the regular first-principles molecular dynamics method. Electronic- and atomic-level information on the catalytic reaction dynamics at reaction temperatures significantly contributes the catalyst design and development. Hence, we also summarized our recent applications of the above quantum chemical molecular dynamics method to the clarification of the methanol synthesis dynamics in this review. 相似文献