• 제목/요약/키워드: Mixed Oxidation State

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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 (Dehydropolycondensation of Aminopenols under the Catalytic Action of Metallic Chelate Compounds (I) Effects of the Solvents and Characteristics of the Oligomers Obtained)

  • 최규석
    • 대한화학회지
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    • 제12권3호
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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

  • 박준범
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2009년도 제38회 동계학술대회 초록집
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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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공액 사슬을 갖는 철 화합물의 전기화학적 특성 (Electrochemical Properties of Diiron Complexes wish Conjugated Chains)

  • 정민철
    • 한국전기전자재료학회논문지
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    • 제15권6호
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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.

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

  • 조경호;박정현;신채호
    • 청정기술
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    • 제16권2호
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    • pp.132-139
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    • 2010
  • 서로 다른 몰비의 Cu-Mn 혼합산화물을 공침법으로 제조하여 $30^{\circ}C$에서 CO 산화반응을 수행하였다. 제조된 촉매는 CO 산화반응에서 반응 활성과 연관시키기 위하여 XRD, $N_2$ 흡착 및 탈착, XPS, $H_2-TPR$ 등의 특성분석을 수행하였다. 제조된 촉매의 질소흡착 등온곡선은 4형태로 7-20 nm크기의 세공이 존재하며, Mn의 함량이 증가함에 따라 BET 표면적은 17에서 $205m^2{\cdot}g^{-1}$ 으로 증가하였다. XPS 분석으로 Cu-Mn 혼합산화물 상의 Cu는 주성분이 2+의 산화상태임을 확인하였고, Mn은 +3과 +4의 산화 상태를 나타냈다. Cu-Mn 촉매의 함량 및 비율에 따른 최적 활성을 실험 조사한 결과, $30^{\circ}C$의 반응온도에서 Cu/(Cu+Mn)의 몰비가 0.5일 때 가장 좋은 활성을 나타냈으며, 이를 기준으로 화산형 형태의 반응 곡선을 나타냈다. 수분 존재하의 CO 산화반응은 활성점에 수분과 CO의 경쟁흡착으로 촉매의 활성을 감소시켰으며 최종적으로는 활성금속 성분과 하이드록실 그룹을 형성하였기 때문이다.

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

  • 김명희;김은경
    • Journal of Nutrition and Health
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    • 제44권6호
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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.

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

  • 이상훈;천찬란;심지애
    • 자원환경지질
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    • 제36권5호
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    • pp.349-356
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    • 2003
  • 최근 산업활동의 종류가 점차 복잡해지면서 오염물질의 종류도 많아지고 있으며 오염물질의 성상도 점차 복합화하고 있다. 이런 경향은 과거 단일 물질에 의한 오염에서 점차 유기물과 중금속이 동시에 오염되는 것과 같은 혼합 오염형태가 증가하고 있는데서 인지된다. 본 연구는 유류와 중금속이 동시에 오염된 지역에서 유류분해에 따른 혐기성 환경전환이 비소의 농도와 화학종에 어떤 영향을 미치며 그 결과가 위해성과 정화작용에 어떤 영향을 미치는지를 확인하고자 하였다. 충적대수층에서 채취한 사질토양을 tetradecane으로 오염시킨 후 As(III)과 As(V)를 각각 1:1, As(III)로만 그리고 As(V)로만 등으로 혼합비율을 달리하여 오염시킨 후 마이크로코즘을 제작하여 혐기성 반응기안에 방치, 60일간 운전하였다. 매 10일마다 마이크로코즘을 개방하여 유기물, As(III) 및 As(V)의 농도 그리고 Fe, Mn의 농도변화를 측정하였다. 전체 As 농도에 대한 As(III)의 비율, As(III) 자체의 농도 변화 그리고 유기물 분해경향 등을 바탕으로 유기물분해에 따라 As(III)의 증가에 영향을 미치는 것이 확인되었다. Fe, Mn의 환원에 따른 As의 산화와 유기물 분해에 따른 환원이 서로 상충할 수 있으며 실제 분해 단계에 따라 어느 한쪽의 작용이 우세해지는 것으로 판단된다. 즉, Fe, Mn의 환원은 유기물의 분해에 의해 억제되었으며 유기물 분해가 상당히 진행 된 이후 Fe, Mn의 혐기성 용출이 일어나는 것으로 생각된다. 본 연구 결과는 혼합오염지역의 경우 유기물분해는 비소종의 화학형태에 영향을 미칠 것으로 예상되며 만약 As(III)의 비율이 증가할 경우 비소종의 위해성은 증가하게 될 것으로 판단되며 점차 증가하고 있는 혼합오염물 지역에 대한 정량적 위해성 평가가 요구된다.

Electronic Structure Study of Gold Selenides

  • 이왕로;정동운
    • Bulletin of the Korean Chemical Society
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    • 제20권2호
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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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    • 제17권2호
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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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    • 제48권3호
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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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    • 제22권5호
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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.