• Title/Summary/Keyword: Mixed Oxidation State

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Dehydropolycondensation of Aminopenols under the Catalytic Action of Metallic Chelate Compounds (I) Effects of the Solvents and Characteristics of the Oligomers Obtained (金屬킬레이트化合物의 觸媒作用에 依한 Aminophenol 類의 酸化的 重縮合反應 (Ⅰ) 溶媒의 效果와 生成重合體의 特性)

  • Choi, Kyu-Suck
    • Journal of the Korean Chemical Society
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    • v.12 no.3
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    • pp.114-120
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    • 1968
  • Fe-EDTA complex, which is easily formed when Fe salt and EDTA.2Na are mixed in the aqueous medium, is found to be a very effective catalyst in the dehydropolycondensation of aminophenols. In the dehydropolycondensation of aminophenols, the catalyst, Fe(Ⅲ)-EDTA complex (higher oxidation state) is reduced to less stable Fe(Ⅱ)-EDTA complex (lower oxidation state), and the latter is easily oxidized by air to the original higher oxidation state complex, therefore the catalytic action of Fe-EDTA complex is found to be recycled effectively. Under the catalytic action of the above mentioned complex, p-aminophenol is polymerized in the aqueous medium to form the oligomers of p-aminophenol, which the degree of polymerization to be 5 or more. The oligomers formed contain partly quinone nucleus as well as amino and hydroxyl groups. In this study, the effects of the solvents and characteristics of the oligomers are discussed. These types of polymerizations catalyzed by the metallic chelate compounds are considered to be very closely related to the reactions in the living matters.

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The structures and catalytic activities of metallic nanoparticles on mixed oxide

  • Park, Jun-Beom
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.02a
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    • pp.339-339
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    • 2010
  • The metallic nanoparticles (Pt, Au, Ag. Cu, etc.) supported on ceria-titania mixed oxide exhibit a high catalytic activity for the water gas shift reaction ($H_2O\;+\;CO\;{\leftrightarrow}\;H_2\;+\;CO_2$) and the CO oxidation ($O_2\;+\;2CO\;{\leftrightarrow}\;2CO_2$). It has been speculated that the high catalytic activity is related to the easy exchange of the oxidation states of ceria ($Ce^{3+}$ and $Ce^{4+}$) on titania, but very little is known about the ceria titanium interaction, the growth mode of metal on ceria titania complex, and the reaction mechanism. In this work, the growth of $CeO_x$ and Au/$CeO_x$ on rutile $TiO_2$(110) have been investigated by Scanning Tunneling Microscopy (STM), Photoelectron Spectroscopy (PES), and DFT calculation. In the $CeO_x/TiO_2$(110) systems, the titania substrate imposes on the ceria nanoparticles non-typical coordination modes, favoring a $Ce^{3+}$ oxidation state and enhancing their chemical activity. The deposition of metal on a $CeO_x/TiO_2$(110) substrate generates much smaller nanoparticles with an extremely high activity. We proposed a mechanism that there is a strong coupling of the chemical properties of the admetal and the mixed-metal oxide: The adsorption and dissociation of water probably take place on the oxide, CO adsorbs on the admetal nanoparticles, and all subsequent reaction steps occur at the oxide-admetal interface.

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Electrochemical Properties of Diiron Complexes wish Conjugated Chains (공액 사슬을 갖는 철 화합물의 전기화학적 특성)

  • ;Micheal b. Sponsler
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.15 no.6
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    • pp.511-517
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    • 2002
  • The complex 1 $([Cp*Fe(CO)_2]_2-(\mu-CH=CH-CH=CH))$ which have butadiene as a bridge were synthesized from $Cp*(CO)_2FeK$ and cis-3,4-dichlorocyclobutene. The derivatives of complex 1 where one or two carbonyl groups are replaced by phosphine ligands have been prepared by photochemical substitution. The new derivatives $([Cp*Fe(L)_2]_2-(\mu-CH=CH-CH=CH))$ where L = $(Ph_2PCH_2CH_2PPh_2)$ and $([Cp*Fe(CO)(L)]_2-(\mu-CH=CH-CH=CH))$ where L : $PPh_3$ have been characterized from $^^1H-$, $^^13C-$,$^^31P-NMR$ and elemental analysis. Obtained complexes have been studied in electrochemical experiment and UV/VIS-near-IR. The mixed-valence radical cation forms of complex 2, 3 species were found to be delocalized as the Class III. Based on the separation of the waves ($\triangle E$ : 0.470 ~ 0.605 V), the efficiency of electronic communication between two metal centers of cation species leading to stabilization relative to neutral species. The phosphine-substitute complexes (2, 3) displays two reversible oxidation waves and oxidation state of metal centers-dependent color change, electrochromism, was observed from yellow to orange and deep blue in methylene chloride.

Low Temperature CO Oxidation over Cu-Mn Mixed Oxides (Cu-Mn 혼합산화물 상에서 일산화탄소의 저온산화반응)

  • Cho, Kyong-Ho;Park, Jung-Hyun;Shin, Chae-Ho
    • Clean Technology
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    • v.16 no.2
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    • pp.132-139
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    • 2010
  • The Cu-Mn mixed oxide catalysts with different molar ratios of Cu/(Cu+Mn) prepared by co-precipitation method have been investigated in CO oxidation at $30^{\circ}C$. The catalysts used in this study were characterized by X-ray Diffraction (XRD), $N_2$ sorption, X-ray photoelectron spectroscopy (XPS), and $H_2$-temperature programmed reduction $(H_2-TPR)$ to correlate with catalytic activities in CO oxidation. The $N_2$ adsorption-desorption isotherms of Cu-Mn mixed oxide catalysts showed a type 4 having pore range of 7-20 nm and BET surface area was increased from 17 to $205\;m^2{\cdot}g^{-1}$ with increasing of Mn content. The XPS analysis showed the surface oxidation state of Cu and Mn represented $Cu^{2+}$and the mixture of $Mn^{3+}$ and $Mn^{4+}$, respectively. Among the catalysts studied here, Cu/(Cu+Mn) = 0.5 catalyst showed the highest activity at $30^{\circ}C$ in CO oxidation and the catalytic activity showed a typical volcano-shape curve with respect to Cu/(Cu+Mn) molar ratios. The water vapor showed a prohibiting effect on the efficiency of the catalyst which is due to the competitive adsorption of carbon monoxide on the active sites of catalyst surface and finally the formation of hydroxyl group with active metals.

Thermic Effect of Food and Macronutrient Oxidation Rate in Men and Women after Consumption of a Mixed Meal (성인 남녀의 식사성 발열효과 및 식후 영양소 산화율)

  • Kim, Myung-Hee;Kim, Eun-Kyung
    • Journal of Nutrition and Health
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    • v.44 no.6
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    • pp.507-517
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    • 2011
  • The purpose of this study was to investigate the effects of gender on the thermic effect of food and substrate oxidation rate during 5 hours after a mixed meal. Twenty healthy college students (10 males and 10 females) aged 20-26 years participated in this study. The energy contents of the experimental diets were 775 kcal and 627 kcal for males and females respectively, which were 30% of individual energy requirements and were composed of 65/15/20% as the proportion of carbohydrate/protein/fat. Resting and postprandial energy expenditure and substrate oxidation rates were measured with indirect calorimetry in the fasting state and every 30 min for 5 hours after meal consumption. Thermic effects of food expressed as ${\Delta}AUC$ and TEF% were not significantly different between males and females. However, TEF% adjusted for body weight and fat-free mass in males (0.095% and 0.120%) were significantly lower than those in females (0.152% and 0.213%)(p < 0.05). The total amount of carbohydrate oxidized was significantly lower in males than that in females (58.6 vs. 86.6 mg/kcal energy intake/5 h, p < 0.05). In contrast, the total amount of fat oxidized was significantly higher in males than that in females after the meal (32.9 vs. 17.2 mg/kcal energy intake/5 h, p < 0.01). These results indicate that gender affects the thermic effects of food and the substrate oxidation rate after a meal. The results show that males use relatively less carbohydrate and more fat as an energy source after a meal than that of females.

Preliminary Study on Arsenic Speciation Changes Induced by Biodegradation of Organic Pollutants in the Soil Contaminated with Mixed Wastes (유기물분해에 따른 유류${\cdot}$중금속 복합오염토양내 비소화학종 변화의 기초연구)

  • 이상훈;천찬란;심지애
    • Economic and Environmental Geology
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    • v.36 no.5
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    • pp.349-356
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    • 2003
  • As industrial activities are growing, pollutants found in the contaminated land are getting diverse. Some contaminated areas are subject to mixed wastes containing both organic and inorganic wastes such as hydrocarbon and heavy metals. This study concerns with the influence of the degradation of organic pollutants on the coexisting heavy metals, expecially for As. As mainly exists as two different oxidation state; As(III) and As(V) and the conversion between the two chemical forms may be induced by organic degradation in the soil contaminated by mixed wastes. We operated microcosm in an anaerobic chamber for 60 days, using sandy loam. The soils in the microcosm are artificially contaminated both by tetradecane and As, with different combination of As(III) and As(V); As(III):As(V) 1:1, As(III) only and As(V) only. Although not systematic, ratio of As(III)/As(Total) increase slightly at the later stage of experiment. Considering complicated geochemical reactions involving oxidation/reduction of organic materials, Mn/Fe oxides and As, the findings in the study seem to indicate the degradation of the organics is connected with the As speciation. That is to say, the As(V) can be reduced to As(III) either by direct or indirect influence induced by the organic degradation. Although Fe and Mn are good oxidising agent for the oxidation of As(III) to As(V), organic degradation may have suppressed reductive dissolution of the Fe and Mn oxides, causing the organic pollutants to retard the oxidation of As(III) to As(V) until the organic degradation ceases. The possible influence of organic degradation on the As speciation implies that the As in mixed wastes may be have elevated toxicity and mobility by partial conversion from As(V) to As(III).

Electronic Structure Study of Gold Selenides

  • 이왕로;정동운
    • Bulletin of the Korean Chemical Society
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    • v.20 no.2
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    • pp.147-149
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    • 1999
  • The electronic structures of α- and β-gold selenides are studied. α- and β-AuSe are known as mixed valence compounds having linear (AuSe2, Au+) and square-planar (AuSe4, Au3+) units in their structure simultaneously. Our EHTB calculations, however, show that the oxidation states of Au in α- and β-AuSe are both close to +1. This is because the frontier orbitals are largely made up of Se p-orbitals and Au d-orbitals that lie well below the Fermi level. Our results are consistent with the recent X-ray absorption spectroscopy study on AuSe which show that all Au in the compound exhibit a monovalent state independent of their chemical environments.

The Oxidation of Magnetic Particles in Medicinal Ointment

  • Kim, Eng-Chan
    • Journal of Magnetics
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    • v.17 no.2
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    • pp.83-85
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    • 2012
  • Magnetic particles in a novel, wound-healing ointment were studied using M$\ddot{o}$ssbauer spectroscopy and VSM to estimate the stability of the properties of the magnetic particles. The isomer shifts of $Fe_3O_4(A)$ were found to be 0.49-0.56 mm/s relative to iron metal, this indicates that the iron ions in $Fe_3O_4(A)$ are $Fe^{3+}$. On the other hand, the isomer shifts of $Fe_3O_4(B)$ were found to be 0.91-1.13 mm/s relative to iron metal, this shows that the ion state of $Fe_3O_4(B)$ is a mixed state of $Fe^{2+}$ and $Fe^{3+}$. It is noted that this composition, as well as that of the initial pure component in the form of a highly dispersed fraction (${\sim}10\;{\AA}$), differs from the stoichiometric one. It was found that the area ratio of the M$\ddot{o}$ssbauer subspectra of $Fe_3O_4(A)$ / $Fe_3O_4(B)$ taken at 87 and 181 K linearly increased in comparison to the initial pure magnetic particles, but the rate of increase of the area ratio at 181 K was about two times that at 87 K. From the magnetic hyperfine field, despite their small size, the particles exhibit no superparamagnetism.

Determination of Plutonium Present in Highly Radioactive Irradiated Fuel Solution by Spectrophotometric Method

  • Dhamodharan, Krishnan;Pius, Anitha
    • Nuclear Engineering and Technology
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    • v.48 no.3
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    • pp.727-732
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    • 2016
  • A simple and rapid spectrophotometric method has been developed to enable the determination of plutonium concentration in an irradiated fuel solution in the presence of all fission products. An excess of ceric ammonium nitrate solution was employed to oxidize all the valence states of plutonium to +6 oxidation state. Interference due to the presence of fission products such as ruthenium and zirconium, and corrosion products such as iron in the envisaged concentration range, as in the irradiated fuel solution, was studied in the determination of plutonium concentration by the direct spectrophotometric method. The stability of plutonium in +6 oxidation state was monitored under experimental conditions as a function of time. Results obtained are reproducible, and this method is applicable to radioactive samples resulting before the solvent extraction process during the reprocessing of fast reactor spent fuel. An analysis of the concentration of plutonium shows a relative standard deviation of <1.2% in standard as well as in simulated conditions. This reflects the fast reactor fuel composition with respect to uranium, plutonium, fission products such as ruthenium and zirconium, and corrosion products such as iron.

Metabolic Pathways of Hydrogen Production in Fermentative Acidogenic Microflora

  • Zhang, Liguo;Li, Jianzheng;Ban, Qiaoying;He, Junguo;Jha, Ajay Kumar
    • Journal of Microbiology and Biotechnology
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    • v.22 no.5
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    • pp.668-673
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    • 2012
  • Biohydrogen production from organic wastewater by anaerobically activated sludge fermentation has already been extensively investigated, and it is known that hydrogen can be produced by glucose fermentation through three metabolic pathways, including the oxidative decarboxylation of pyruvic acid to acetyl-CoA, oxidation of NADH to $NAD^+$, and acetogenesis by hydrogen-producing acetogens. However, the exact or dominant pathways of hydrogen production in the anaerobically activated sludge fermentation process have not yet been identified. Thus, a continuous stirred-tank reactor (CSTR) was introduced and a specifically acclimated acidogenic fermentative microflora obtained under certain operation conditions. The hydrogen production activity and potential hydrogen-producing pathways in the acidogenic fermentative microflora were then investigated using batch cultures in Erlenmeyer flasks with a working volume of 500 ml. Based on an initial glucose concentration of 10 g/l, pH 6.0, and a biomass of 1.01 g/l of a mixed liquid volatile suspended solid (MLVSS), 247.7 ml of hydrogen was obtained after a 68 h cultivation period at $35{\pm}1^{\circ}C$. Further tests indicated that 69% of the hydrogen was produced from the oxidative decarboxylation of pyruvic acid, whereas the remaining 31% was from the oxidation of NADH to $NAD^+$. There were no hydrogen-producing acetogens or they were unable to work effectively in the anaerobically activated sludge with a hydraulic retention time (HRT) of less than 8 h.