• Title/Summary/Keyword: Oxidation State

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Review of Recent Smog Chamber Studies for Secondary Organic Aerosol (스모그 챔버를 이용한 이차 초미세유기먼지의 최근 연구 동향)

  • Lim, Yong Bin;Lee, Seung-Bok;Kim, Hwajin;Kim, Jin Young;Bae, Gwi-Nam
    • Journal of Korean Society for Atmospheric Environment
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    • v.32 no.2
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    • pp.131-157
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    • 2016
  • A smog chamber has been an effective tool to study air quality, particularly secondary organic aerosol (SOA), which is typically formed by atmospheric oxidation of volatile organic compounds (VOCs). In controlled environments, smog chamber studies have validated atmospheric oxidation by identifying, quantifying and monitoring products with state-of-art instruments (e.g., aerosol mass spectrometer, scanning mobility particle sizer) and provided chemical insights of SOA formation by elucidating reaction mechanisms. This paper reviews types of smog chambers and the current state of smog chamber studies that have accomplished to find pathways of SOA formation, focusing on gas-particle partitioning of semivolatile products of VOC oxidation, heterogeneous reactions on aerosol surface, and aqueous chemistry in aerosol waters (e.g., cloud/fog droplets and wet aerosols). For future chamber studies, then, this paper discusses potential formation pathways of fine particles that East Asia countries (e.g., Korea and China) currently suffer from due to massive formation that gives rise to fatal health problems.

The Study on Location and Adsorbate Interaction for Vanadium Species in $VO^{2+}-SAPO-5$ by Electron Spin Resonance and Electron Spin Echo Modulation Spectroscopies

  • Back Gern-Ho;Park Sung-Gun;Lee Chul-Wee
    • Journal of the Korean Magnetic Resonance Society
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    • v.9 no.2
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    • pp.138-154
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    • 2005
  • Vanadium-incorporated aluminophosphate molecular sieve $VO^{2+}-SAPO-5$ was studied by electron spin resonance (ESR) and electron spin echo modulation (ESEM) spectroscopies to determine the vanadium structure and interaction with various adsorbate molecules. It was found that the main species at low concentration of vanadium is a monomeric vanadium units in square pyramidal or distorted octahedral coordination, both in oxidation state (IV) for the calcined hydrated material and in oxidation state (V) for the calcined material. After calcinations in $O_2$ and exposure to moisture, only species A is observed with reduced intensities. It is suggested as a $VO(H_2O)_3^{2+}$ complex coordinated to two framework oxygen bonded aluminum. When calcined, hydrated $VO^{2+}-}SAPO-5$ is dehydrated at elevated temperature, a species loses its water ligands and transforms to $VO^{2+}$ ions coordinated to two framework oxygens (species B). Species B reduces its intensity, significantly after treatment with $O_2\;at\;600^{\circ}C$ for 5 h, thus suggesting oxidation of $V^{4+}\;to\;V^{5+}$. When dehydrated $VO^{2+}-SAPO-5$ contacts with $D_2O$ at room temperature, the EPR signal of species A is observed. Thus species assumed as a $VO^{2+}(O_f)_2(D_2O)_3$, by considering two framework oxygens. Adsorption of deuterated ethanol, propanol on dehydrated $VO^{2+}_{-}SAPO-5$ result in another new vanadium species E and F, respectively, which are identified as a $VO^{2+}-(CH_3CH_2OD)_3,\;VO^{2+}-(CH_3CH_2CH_2OD)_2$ complex. When deuterated benzene is adsorbed on dehydrated $VO^{2+}-SAPO-5$, another new vanadium species G, identified as a $VO^{2+}-(C_6D_6)$ is observed. Possible coordination geometries of these various complexes are discussed.

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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.

Effect of Carnosine and Related Compounds on Glucose Oxidation and Protein Glycation In Vitro

  • Lee, Beom-Jun;Park, Jae-Hak;Lee, Yong-Soon;Cho, Myung-Haing;Kim, Young-Chul;Hendricks, Deloy G.
    • BMB Reports
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    • v.32 no.4
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    • pp.370-378
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    • 1999
  • The effects of carnosine and related compounds (CRC) including anserine, homocarnosine, histidine, and ${\beta}$-alanine, found in most mammalian tissues, were investigated on in vitro glucose oxidation and glycation of human serum albumin (HSA). Carnosin and anserine were more reactive with D-glucose than with L-lysine. In the presence of $10\;{\mu}M$ Cu (II), although carnosine and anserine at low concentrations effectively inhibited formation of ${\alpha}$-ketoaldehyde from D-glucose, they increased generation of $H_2O_2$ in a dose-dependent manner. Carnosine, homocarnosine, anserine, and histidine effectively inhibited hydroxylation of salicylate and deoxyribose degradation in the presence of glucose and $10\;{\mu}M$ Cu (II). In the presence of 25 mM D-glucose, copper and ascorbic acid stimulated carbonyl formation from HSA. Except for ${\beta}$-alanine, CRC effectively inhibited the copper-catalyzed carbonyl formation from HSA. The addition of 25 mM D-glucose and/or $10\;{\mu}M$ Cu (II) to low density lipoprotein (LDL) increased formation of conjugated dienes. CRC effectively inhibited the glucose and/or copper-catalyzed LDL oxidation. CRC also inhibited glycation of HSA as determined by hydroxymethyl furfural and lysine with free ${\varepsilon}$-amino group. These results suggest that CRC may play an important role in protecting against diabetic complications by reacting with sugars, chelating copper, and scavenging free radicals.

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Revealing Strong Metal Support Interaction during CO Oxidation with Metal Nanoparticle on Reducible Oxide Substrates

  • Park, Dahee;Kim, Sun Mi;Qadir, Kamran;Park, Jeong Young
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.264-264
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    • 2013
  • Strong metal-support interaction effect is an important issue in determining the catalytic ac-tivity for heterogeneous catalysis. In this study, we investigated the support effect and the role of organic capping layers of two-dimensional Pt nanocatalysts on reducible metal oxide supports under the CO oxidation. Several reducible metal oxide supports including CeO2, Nb2O5, and TiO2 thin films were prepared via sol-gel techniques. The structure, chemical state and optical property were characterized using XRD, XPS, TEM, SEM, and UV-VIS spectrometer. We found that the reducible metal oxide supports have a homogeneous thin thickness and crystalline structure after annealing at high temperature showing the different optical band gap energy. Langmuir-Blodgett technique and arc plasma deposition process were employed to ob-tain Pt nanoparticle arrays with capping and without capping layers, respectively on the oxide support to assess the role of the supports and capping layers on the catalytic activity of Pt catalysts under the CO oxidation. The catalytic performance of CO oxidation over Pt supported on metal oxide thin films under oxidizing reaction conditions (40 Torr CO and 100 Torr O2) was tested. The results show that the catalytic activity significantly depends on the metal oxide support and organic capping layers of Pt nanoparticles, revealing the strong metal-support interaction on these nanocatalysts systems.

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Diffusion and Oxidation of Ti3+ Interstitials on a Reduced TiO2 (001) Surface: A Crystal-face Dependency (TiO2 (001)면에서 Ti 결함의 확산과 산화: 결정면에 대한 의존성)

  • Kim, Yu-Kwon
    • Journal of the Korean Vacuum Society
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    • v.21 no.5
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    • pp.242-248
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    • 2012
  • Valence band of a vacuum-reduced $TiO_2$ (001) surface has been carefully examined using synchrotron x-ray photoelectron spectroscopy to investigate variation of the gap state upon oxidation and thermal diffusion of $Ti^{3+}$ interstitials from the bulk. We compare our results with that obtained from $TiO_2$ (110) and aim to address a crystal-face dependency in the oxidation and diffusion rates of $Ti^{3+}$ interstitials. We find very similar behaviors in the oxidation and thermal diffusion rate of $Ti^{3+}$ interstitials between the two crystal faces suggesting a negligible crystal-face dependency in this case.

An Experimental and Modeling Study on the Oxidation Kinetics of Nitric Oxide over Platinum-based Catalysts (백금계 촉매상에서 산화질소(NO)의 산화반응속도에 관한 실험 및 모델링 연구)

  • Kim, Young-Deuk;Jeong, Soo-Jin;Kim, Woo-Seung
    • Transactions of the Korean Society of Automotive Engineers
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    • v.20 no.5
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    • pp.71-80
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    • 2012
  • To improve the $NO_X$ conversion over a SCR (selective catalytic reduction) catalyst, the DOC (diesel oxidation catalyst) is usually placed upstream of the SCR catalyst to enhance the fast SCR reaction ($4NH_3+2NO+2NO_2{\rightarrow}4N_2+6H_2O$) using equimolar amounts of NO and $NO_2$. Here, a ratio of $NO_2/NO_X$ above 50% should be avoided, because the reaction with $NO_2$ only ($4NH_3+4NO+O_2{\rightarrow}4N_2+6H_2O$) is slower than the standard SCR reaction ($4NH_3+4NO+O_2{\rightarrow}4N_2+6H_2O$). In order to accurately predict the performance characteristics of SCR catalysts, it is therefore desired to develop a more simple and reliable mathematical and kinetic models on the oxidation kinetics of nitric oxide over a DOC. In the present work, the prediction accuracy and limit of three different chemical reaction kinetics models are presented to describe the chemicophysical characteristics and conversion performance of DOCs. Steady-state experiments with DOCs mounted on a light-duty four-cylinder 2.0-L turbocharged diesel engine then are performed, using an engine-dynamometer system to calibrate the kinetic parameters such as activation energies and preexponential factors of heterogeneous reactions. The reaction kinetics for NO oxidation over Pt-based catalysts is determined in conjunction with a transient one-dimensional (1D) heterogeneous plug flow reactor (PFR) model with diesel exhaust gas temperatures in the range of 115~$525^{\circ}C$ and space velocities in the range of $(0.4{\sim}6.5){\times}10^5\;h^{-1}$.

Effects of Microbial Iron Reduction and Oxidation on the Immobilization and Mobilization of Copper in Synthesized Fe(III) Minerals and Fe-Rich Soils

  • Hu, Chaohua;Zhang, Youchi;Zhang, Lei;Luo, Wensui
    • Journal of Microbiology and Biotechnology
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    • v.24 no.4
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    • pp.534-544
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    • 2014
  • The effects of microbial iron reduction and oxidation on the immobilization and mobilization of copper were investigated in a high concentration of sulfate with synthesized Fe(III) minerals and red earth soils rich in amorphous Fe (hydr)oxides. Batch microcosm experiments showed that red earth soil inoculated with subsurface sediments had a faster Fe(III) bioreduction rate than pure amorphous Fe(III) minerals and resulted in quicker immobilization of Cu in the aqueous fraction. Coinciding with the decrease of aqueous Cu, $SO_4{^{2-}}$ in the inoculated red earth soil decreased acutely after incubation. The shift in the microbial community composite in the inoculated soil was analyzed through denaturing gradient gel electrophoresis. Results revealed the potential cooperative effect of microbial Fe(III) reduction and sulfate reduction on copper immobilization. After exposure to air for 144 h, more than 50% of the immobilized Cu was remobilized from the anaerobic matrices; aqueous sulfate increased significantly. Sequential extraction analysis demonstrated that the organic matter/sulfide-bound Cu increased by 52% after anaerobic incubation relative to the abiotic treatment but decreased by 32% after oxidation, indicating the generation and oxidation of Cu-sulfide coprecipitates in the inoculated red earth soil. These findings suggest that the immobilization of copper could be enhanced by mediating microbial Fe(III) reduction with sulfate reduction under anaerobic conditions. The findings have an important implication for bioremediation in Cu-contaminated and Fe-rich soils, especially in acid-mine-drainage-affected sites.

Activity and Characteristics of Cu-Mn Oxide Catalysts Supported on γ-Al2O3 (γ-Al2O3에 담지된 Cu-Mn 산화물 촉매의 활성 및 특성)

  • Kim, Hye-jin;Choi, Sung-Woo;Lee, Chang-Seop
    • Korean Chemical Engineering Research
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    • v.44 no.2
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    • pp.193-199
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    • 2006
  • The catalytic oxidation of toluene over $-Al_2O_3$ supported copper-manganese oxide catalysts in the temperature range of $160-280^{\circ}C$ was investigated by employing a fixed bed flow reactor. The catalysts were characterized by BET, scanning electron microscopy (SEM), temperature-programmed reduction(TPR), temperature-programmed oxidation(TPO), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction(XRD) techniques. Catalytic oxidation of toluene was achieved at the below $280^{\circ}C$, and the optimal content of copper and manganese in the catalyst was found to be 15.0 wt%Cu-10.0 wt%Mn. From the TPR/TPO and XPS results, the redox peak of 15 Cu-10 Mn catalyst shifted to the lower temperature, and the binding energy was shifted to the higher binding energy. Furthermore, It is considered that $Cu_{1.5}Mn_{1.5}O_4$ is superior to Mn oxides and CuO in the role as active factor of catalysts from the XRD results and also catalytic activities are dependent on the redox ability and high oxidation state of catalysts.

Effect of promoter on platinum catalyst for oxidation of VOCs (VOCs 산화반응에서 Pt 촉매에 대한 조촉매의 영향)

  • Kim, Moon-Chan;Shin, Jin-Sil
    • Analytical Science and Technology
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    • v.19 no.5
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    • pp.422-432
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    • 2006
  • The volatile organic compounds(VOCs) have been recognized as a major contributor to air pollution. The catalytic oxidation is one of the most important processes for VOCs destruction due to getting high efficiency at low temperature. In this study, monometallic Pt and bimetallic Pt-Ru, Pt-Ir were supported to ${\gamma}-Al_2O_3$. Xylene, toluene and MEK were used as reactants. The monometallic or bimetallic catalysts were prepared by the excess wetness impregnation method and were characterized by XRD, XPS, TEM and BET analysis. As a result, Pt-Ru, Pt-Ir bimetallic catalysts showed higher conversion than Pt monometallic catalyst. Pt-Ir bimetallic catalyst showed the highest conversion on the ${\gamma}-Al_2O_3$ support. In the VOCs oxidation, Pt-Ru, Pt-Ir bimetallic catalyst had multipoint active sites, so it improved the range of Pt metal state. Therefore, bimetallic catalysts showed higher conversion of VOCs than monometallic ones. In this study, the use of small amount of Ru, Ir to Pt promoted oxidation conversion of VOCs.