• Title/Summary/Keyword: Reaction Oxygen

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Influence of Oxyfluorination on Properties of Polyacrylonitrile (PAN)- Based Carbon Fibers

  • Lim, In-Seub;Yoo, Seung-Hwa;Park, Il-Nam;Lee, Young-Seak
    • Carbon letters
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    • v.5 no.1
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    • pp.12-17
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    • 2004
  • In this study, the oxyfluorination of PAN-based carbon fibers was undertaken at room temperature using fluorine-oxygen mixtures, and the influence of oxyfluorination on properties was investigated. The surface characteristics of the modified fiber were determined by using X-ray photoelectron spectroscopy (XPS) and dynamic contact angle analyzer. The oxyfluorination of carbon fibers was one of the more effective methods to increase surface wettability by the formation of semicovalent C-F bond and C-O bond depending on reaction conditions. When oxygen mole fraction is increased from 0.5 to 0.9, it is probable that attached fluorine atoms at the surface of the fibers reacted with other components. As increased oxyfluorination time and decreased its pressures, semi-covalent peak is increased at 0.5 of oxygen mole fraction. The total surface free energy of oxyfluorinated carbon fibers decreased with increasing oxygen mole fraction over 0.5. These results indicate that the surface of carbon fibers became much more hydrophilic after the short oxyfluorination. The surface free energy of oxyfluorinated carbon fibers progressively decreased after 10 min treatment. The polar components of surface free energies were however, significantly higher for all oxyfluorinated samples than that for the untreated carbon fiber.

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Charge/Discharge Characteristics of $SnO_2$ thin film as an anode of thin film secondary battery for microelectromechanical system device (Microelectromechnical system 소자를 위한 박막형 2차전지용 $SnO_2$ 음극박막의 충방전 특성 평가)

  • 남상철;조원일;전은정;신영화;윤영수
    • Journal of the Korean Vacuum Society
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    • v.9 no.1
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    • pp.36-41
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    • 2000
  • $SnO-2$ thin films for thin film secondary battery anode were deposited n glass substrate with stain-less steel collector and charge/discharge experiments were conducted to investigate feasibility of $SnO-2$ thin film as a new anode material. The as-deposited films were pure $SnO-2$ phase which is not related to deposition condition. The grain size on the surface of as-deposited films increased with increase of oxygen partial pressure. However, the grain size did not show any change above oxygen partial pressure of 80:20. The surface roughness of the as-deposited films increased after decreasing because of resputtering effect of oxygen negative ion in plasma. All films showed typical $SnO-2$ anode characteristics which has a side effect at the first cycle, which is not related to the deposition condition. The charge/discharge experiments of 200cycles indicated that capacity of $SnO-2$ films depended on oxygen contents and surface roughness. The cycle characteristics was determined by initial charge/discharge reaction. The $SnO-2$ film with low initial capacity showed more stable cycle characteristics than film with high initial capacity.

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CO Adsorption and Reaction on Clean and Zn-deposited Au(211) surface

  • Jo, Sang-Wan;Mbuga, F.;Ogasawara, H.;Nilsson, A.
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.08a
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    • pp.128.2-128.2
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    • 2013
  • Crucially, effective catalysts must be capable of efficiently catalyzing the protonation of adsorbed CO to adsorbed CHO or COH. One of the strategies is alloying with metals with higher oxygen affinity and Au-Zn alloy is one of the best candidates. At first, we made Au-Zn alloy using vacuum evaporating method. Zn was deposited on the Au(211) surface and the amount was estimated by X-ray photoelectron spectroscopy (XPS) using the relative sensitivity of Au 4f and Zn 3d. We investigated CO adsorption on a clean Au(211) and Au-Zn alloy using temperature-programmed desorption (TPD) and XPS. From the TPD results, we can conclude that the presence of the particular step sites at the Au(211) surface imparts stronger CO bonding and Zn atoms are sitting on the step sites at the Au(211) when Zn is deposited. The XPS results show the oxygen atoms of CO bond Zn atoms on Au-Zn surface. It should be an evidence that alloying Zn atoms that has high oxygen affinity into an electrocatalyst may allow CHO* to bind to the surface through both the carbon and oxygen atoms.

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The Effect of Polarizability on Rate and Reaction Mechanism: Reactions of S-Aryl Substituted Thiobenzoates with $HO-$ and Aryloxide Ions

  • Ik-Hwan Um;Sang-Eun Chun;Dong-Sook Kwon
    • Bulletin of the Korean Chemical Society
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    • v.12 no.5
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    • pp.510-514
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    • 1991
  • Second-order rate constants have been determined spectrophotometrically for reactions of S-p-nitrophenyl substituted thiobenzoates with various phenoxide ions and S-aryl substituted thiobenzoates with $HO^-$ ion. Thiol esters have been found to be more reactive than the corresponding oxygen esters toward phenoxide ions. The high reactivity of thiol esters relative to oxygen esters becomes insignificant as the basicity of the nucleophile increases. Furthermore, the highly basic $HO^-$ ion is less reactive toward thiol esters than oxygen esters. The significant dependence of the reactivity of thiol esters on the basicity of nucleophiles has been attributed to the nature of the HSAB principle. The present kinetic study has also revealed that the reactivity of thiol esters compared to oxygen esters is not so pronounced as expected based on the enhanced nucleofugicity of thiol esters. However, the effects of substituents in the nucleophile and in the acyl moiety of the substrate on rate appear to be significant. These kinetic results have led to a conclusion that the present reactions proceed via a rate-determining formation of a tetrahedral intermediate followed by a fast breakdown of it. The magnitude of the ${\beta}$ values shows no tendency either to increase or to decrease with the intrinsic reactivity of the reagents. The constancy of ${\beta}$ values in the present system is suggestive that the RSP should have limited applicability.

Kinetics and Oxygen Vacancy Mechanism of the Oxidation of Carbon Monoxide on Perovskite$Nd_{1-x}Sr_xCoO_{3-y}$ Solutions as a Catalyst

  • Dong Hoon Lee;Keu Hong Kim
    • Bulletin of the Korean Chemical Society
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    • v.15 no.8
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    • pp.616-622
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    • 1994
  • The oxidation of carbon monoxide by gaseous oxygen in the presence of a powdered $Nd_{1-x}Sr_xCoO_{3-y}$ solid solution as a catalyst has been investigated in the temperature range from 150$^{\circ}$C to 300$^{\circ}$C under various CO and $O_2$ partial pressures. The site of Sr substitution, nonstoichiometry, structure, and microstructure were studied by means of powder X-ray diffraction and infrared spectroscopy. The electrical conductivity of the solid solution has been measured at 300$^{\circ}$C under various CO and $O_2$ partial pressures. The oxidation rates have been correlated with 1.5-and 1.2-order kinetics with and without a $CO_2$ trap, respectively; first-and 0.7 order with respect to CO and 0.5-order to $O_2$. For the above reaction temperature range, the activation energy is in the range from 0.25 to 0.35 eV/mol. From the infrared spectroscopic, conductivity and kinetic data, CO appears essentially to be adsorbed on the lattice oxygens of the catalyst, while $O_2$ adsorbs as ions on the oxygen vacancies formed by Sr substitution. The oxygen vacancy mechanism of the CO oxidation and the main defect of $Nd_{1-x}Sr_xCoO_{3-y}$ solid solution are supported and suggested from the agreement between IR data, conductivities, and kinetic data.

Numerical Study of Evaporation and Ignition of in-line Array Liquid Droplets (액적 배열의 증발과 착화에 관한 수치해석적 연구)

  • 김충익;송기훈
    • Fire Science and Engineering
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    • v.13 no.1
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    • pp.37-47
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    • 1999
  • The spreading fire of very small floating particles after they are ignited is fast and t therefore dangerous. The research on this area has been limited to experiments and global simulations which treat them as dusts or gaseous fuel with certain concentration well m mixed with air. This research attempted micro-scale analysis of ignition of those particles modeling them as liquid droplets. For the beginning, the in-line array of fuel droplets is modeled by two-dimensional, unsteady conservation equations for mass, momentum, energy and species transport in the gas phase and an unsteady energy equation in the liquid phase. They are solved numerically in a generalized non-orthogonal coordinate. The single step chemical reaction with reaction rate controlled by Arrhenius’ law is assumed to a assess chemical reaction numerically. The calculated results show the variation of temperature and the concentration profile with time during evaporation and ignition process. Surrounding oxygen starts to mix with evaporating fuel vapor from the droplet. When the ignition condition is met, the exothermic reactions of the premixed gas initiate a and burn intensely. The maximum temperature position gradually approaches the droplet surface and maximum temperature increases rapidly following the ignition. The fuel and oxygen concentration distributions have minimum points near the peak temperature position. Therefore the moment of ignition seems to have a premixed-flame aspect. After this very short transient period minimum points are observed in the oxygen and fuel d distributions and the diffusion flame is established. The distance between droplets is an important parameter. Starting from far-away apart, when the distance between droplets decreases, the ignition-delay time decreases meaning faster ignition. When they are close and after the ignition, the maximum temperature moves away from the center line of the in-line array. It means that the oxygen at the center line is consumed rapidly and further supply is blocked by the flame. The study helped the understanding of the ignition of d droplet array and opened the possibility of further research.

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Silver nanowires and nanodendrites synthesized by plasma discharge in solution for the catalytic oxygen reduction in alkaline media

  • Kim, Hoe-Geun;Song, Myeon-Gyu;Kim, Dong-U;Lee, Sang-Yul
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 2018.06a
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    • pp.62-62
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    • 2018
  • Pt is still considered as one of the most active electrocatalysts for ORR in alkaline fuel cells. However, the high cost and scarcity of Pt hamper the widespread commercialization of fuel cells. As a strong candidate for the replacement of Pt catalyst, silver (Ag) has been extensively studied due to its high activity, abundance, and low cost. Ag is more stable than Pt in the pH range of 8~14 as the equilibrium potential of Ag/Ag+ being ${\approx}200mV$ higher than that of Pt/PtO. However, Ag is the overall catalytic activity of Ag for oxygen reduction reaction(ORR) is still not comparable to Pt catalyst since the surface Ag atoms are approximately 10 times less active than Pt atoms. Therefore, further enhancement in the ORR activity of Ag catalysts is necessary to be competitive with current cutting-edge Pt-based catalysts. We demonstrate the architectural design of Ag catalysts, synthesized using plasma discharge in liquid phase, for enhanced ORR kinetics in alkaline media. An attractive feature of this work is that the plasma status controlled via electric-field could form the Ag nanowires or dendrites without any chemical agents. The plasma reactor was made of a Teflon vessel with an inner diameter of 80 mm and a height of 80 mm, where a pair of tungsten(W) electrodes with a diameter of 2 mm was placed horizontally. The stock solutions were made by dissolving the 5-mM AgNO3 in DI water. For the synthesis of Agnanowires, the electricfield of 3.6kVcm-1 in a 200-ml AgNO3 aqueous solution was applied across the electrodes using a bipolar pulsed power supply(Kurita, Seisakusyo Co. Ltd). The repetition rate and pulse width were fixed at 30kHz and 2.0 us, respectively. The plasma discharge was carried out for a fixed reaction time of 60 min. In case of Ag nanodendrites, the electric field of 32kVcm-1 in a 200-ml AgNO3 aqueous solution was applied and other conditions were identical to the plasma discharge in water in terms of electrode configuration, repetition rate and discharge time. Using SEM and STEM, morphology of Ag nanowires and dendrites were investigated. With 3.6 kV/cm, Ag nanowire was obtained, while Ag dendrite was constructed with 32 kV/cm. The average diameter and legth of Ag nanowireses were 50 nm and 3.5 um, and thoes values of Ag dendrites were 40 nm and 3.0 um. As a results of XPS analysis, the surface defects in the Ag nanowires facilitated O2 incorporation into the surface region via the interaction between the oxygen and the electron cloud of the adjacent Ag atoms. The catalytic activity of Ag for oxygen reduction reaction(ORR) showed that the catalytic ORR activity of Ag nanowires are much better than Ag nanodendrites, and electron transfer number of Ag nanowires is similar to that of Pt (${\approx}4$).

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Synthesis of CoFe2O4 Nanoparticles as Electrocatalyst for Oxygen Evolution Reaction (산소 발생 반응 용 전기화학촉매로 사용되는 CoFe2O4 나노 입자 합성 및 특성 분석)

  • Lee, Jooyoung;Kim, Geulhan;Yang, Juchan;Park, Yoo Sei;Jang, Myeong Je;Choi, Sung Mook
    • Journal of the Korean Electrochemical Society
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    • v.23 no.4
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    • pp.97-104
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    • 2020
  • One of the main challenges of electrochemical water splitting technology is to develop a high performance, low cost oxygen-evolving electrode capable of substituting a noble metal catalyst, Ir or Ru based catalyst. In this work, CoFe2O4 nanoparticles with sub-44 nmsize of a inverse spinel structure for oxygen evolution reaction (OER) were synthesized by the injection of KNO3 and NaOH solution to a preheated CoSO4 and Fe(NO3)3 solution. The synthesis time of CoFe2O4 nanoparticles was controlled to control particle and crystallite size. When the synthesis time was 6 h, CoFe2O4 nanoparticles had high conductivity and electrochemical surface area. The overpotential at current denstiy of 10 mA/㎠ and Tafel slope of CoFe2O4 (6h) were 395 mV and 52 mV/dec, respectively. In addition, the catalyst showed excellent durability for 18 hours at 10 mA/㎠.

Fabrication and Characterization of NiCo2O4/Ni Foam Electrode for Oxygen Evolution Reaction in Alkaline Water Splitting (알칼라인 수전해 산소 발생 반응을 위한 NiCo2O4/Ni foam 전극 제조 및 특성 평가)

  • Kwon, Minsol;Go, Jaeseong;Lee, Yesol;Lee, Sungmin;Yu, Jisu;Lee, Hyowon;Song, Sung Ho;Lee, Dongju
    • Journal of Powder Materials
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    • v.29 no.5
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    • pp.411-417
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    • 2022
  • Environmental issues such as global warming due to fossil fuel use are now major worldwide concerns, and interest in renewable and clean energy is growing. Of the various types of renewable energy, green hydrogen energy has recently attracted attention because of its eco-friendly and high-energy density. Electrochemical water splitting is considered a pollution-free means of producing clean hydrogen and oxygen and in large quantities. The development of non-noble electrocatalysts with low cost and high performance in water splitting has also attracted considerable attention. In this study, we successfully synthesized a NiCo2O4/NF electrode for an oxygen evolution reaction in alkaline water splitting using a hydrothermal method, which was followed by post-heat treatment. The effects of heat treatment on the electrochemical performance of the electrodes were evaluated under different heat-treatment conditions. The optimized NCO/NF-300 electrode showed an overpotential of 416 mV at a high current density of 50 mA/cm2 and a low Tafel slope (49.06 mV dec-1). It also showed excellent stability (due to the large surface area) and the lowest charge transfer resistance (12.59 Ω). The results suggested that our noble-metal free electrodes have great potential for use in developing alkaline electrolysis systems.

Catalytic Behavior of Ni/CexZr1-xO2-Al2O3 Catalysts for Methane Steam Reforming: The CexZr1-xO2 Addition Effect on Water Activation (메탄 습식 개질 반응용 Ni/CexZr1-xO2-Al2O3 촉매의 반응 특성: CexZr1-xO2 첨가에 의한 물 활성화 효과)

  • Haewon Jung;Huy Nguyen-Phu;Mingyan Wang;Sang Yoon Kim;Eun Woo Shin
    • Korean Chemical Engineering Research
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    • v.61 no.3
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    • pp.479-486
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    • 2023
  • In this study, we investigated the effect of the CexZr1-xO2 (CZ) addition onto Ni/Al2O3 catalysts on the catalytic performance in methane steam reforming. In the reaction results, the CZ-added Ni/Al2O3 catalyst showed higher CH4 conversion and H2 yield under the same reaction conditions than Ni/Al2O3. From the characterization data, the two catalysts had similar support porosity and Ni dispersion, confirming that the two properties could not determine the catalytic performance. However, the oxygen vacancy over the CZ-added Ni/Al2O3 catalyst induced an efficient steam activation at low reaction temperatures, resulting in an increase in the catalytic activity and H2 yield.