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Adsorptions and Dissociations of Nitric Oxides at Metalloporphyrin Molecules on Metal Surfaces: Scanning Tunneling Microscopy and Spectroscopy Study

  • Kim, Ho-Won;Chung, Kyung-Hoon;Kahng, Se-Jong
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.08a
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    • pp.108-108
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    • 2011
  • Organometallic complexes containing unpaired spins, such as metalloporphyrin or metallophthalocyanine, have extensively studied with increasing interests of their promising model systems in spintronic applications. Additionally, the use of these complexes as an acceptor molecule in chemical sensors has recently received great attentions. In this presentation, we have investigated adsorption of nitric oxide (NO) molecules at Co-porphyrin molecules on Au(111) surfaces with scanning tunneling microscopy and spectroscopy at low temperature. At the location of Co atom in Co-porphyrin molecules, we could observe a Kondo resonance state near Fermi energy in density of states (DOS) before exposing NO molecules and the Kondo resonance state was disappeared after NO exposing because the electronic spin structure of Co-porphyrin were modified by forming a cobalt-NO bonding. Furthermore, we could locally control the chemical reaction of NO dissociations from NO-CoTPP by electron injections via STM probe. After dissociation of NO molecules, the Kondo resonance state was recovered in density of state. With a help of density functional theory (DFT) calculations, we could understand that the modified electronic structures for NO-Co-porphyrin could be occurred by metal-ligand hybridization and the dissociation mechanisms of NO can be explained in terms of the resonant tunneling process via molecular orbitals.

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Synthesis and E-Beam-Mediated Gas Phase Fragmentation of Thiol-Containing Furoxans for Nanopatterned Alkyne Formation on Gold Surface

  • Koo, Hyun-Seo;Park, Kyung-Moon;Hwang, Kwang-Jin
    • Bulletin of the Korean Chemical Society
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    • v.31 no.12
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    • pp.3583-3587
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    • 2010
  • Furoxanthiols PFT and BPFT possessing thiomethyl or thiobenzyl groups in the furoxan ring were designed and synthesized as potential light-sensitive alkyne precursors on a gold surface. The synthesis of thiofuroxans PFT and BPFT was performed from the corresponding halofuroxans 1b and 2c, respectively, by the substitution with potassium thioacetate in ethyl acetate/ethanol or DMF, followed by basic hydrolysis as the key reactions. Electron-beammediated fragmentation of furoxans 1c and 2d in a mass spectrometer afforded the corresponding aryl alkyne fragments, with the evolution of NO in high preference. In the cases of thiofuroxans PFT and BPFT, carbon-sulfur bond cleavage was observed as a representative fragmentation, producing M-SH and M-SAc peaks, which competed with the release of NO. In the fragmentation of mono-aryl furoxan 1c, the release of molecule of NO was predominately observed to produce an M-NO fragment as a base peak by the formation of trimembered thiiranium or azirine intermediate.

$DeNO_{x}$ Performance of Activated Carbon Catalysts Regenerated by Surfactant Solution (계면활성제 수용액에 의해 재생된 활성탄 촉매의 탈질 성능)

  • Park, Hye-Min;Park, Young-Kwon;Jeon, Jong-Ki
    • Korean Chemical Engineering Research
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    • v.49 no.6
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    • pp.739-744
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    • 2011
  • Activated carbon SCR(CSCR) catalyst that is used to remove $NO_x$ in exhaust gas including boron discharged from the production process of liquid crystal display(LCD) shows deactivation when boron is deposited to block the pores within the catalyst or to cover its active sites. The spent carbon catalyst is regenerated by washing with various surfactants, drying and calcination. For comparison of the physical and chemical properties before and after the regeneration with the variables, type of surfactants and calcination condition, element analysis by ICP, $N_{2}$ adsorption were conducted. $DeNO_{x}$ in SCR with $NH_3$ was carried out in a fixed bed reactor at $120^{\circ}C$. The activated carbon catalyst regenerated through washing with a non-ionic surfactant in $H_{2}O$ at $90^{\circ}C$ and calcination under $N_{2}$ gas at $550^{\circ}C$ shows similar level of surface area and $NO_x$ removal efficiency with those of fresh catalyst.

A Study on Subchronic Inhalation Toxicity of Isoprene Using Sprague-Dawely Rats (Isoprene 아급성 흡입독성 연구)

  • Chung, Yong Hyun;Lee, Sung Bae;Han, Jeong Hee;Kang, Min Gu;Kim, Jong Kyu;Rim, Kyung Taek;Yang, Jung Sun
    • Journal of Korean Society of Occupational and Environmental Hygiene
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    • v.21 no.2
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    • pp.73-81
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    • 2011
  • The purpose of this study was to obtain scientific information regarding classification and health hazards that may result from a 13 weeks inhalation exposure of isoprene in Sprague-Dawley (SD) rats. The testing method was conducted in accordance with OECD guidelines for the testing of chemicals No. 413. The Rats were divided into 4 groups (10 male and 10 female rats in each group) and exposed to 0, 360, 1,620, 7,300 ppm isoprene in each exposure chamber for 6 h/day, 5 days/week, for 13 weeks. As a result, there were no mortality or abnormality during the period of study and did not show any significant changes of body weight. There were no dose response changes in urinalysis, hematological and serum biochemical value examination. Relative organ weight was increased significantly the right kidney in 7,300 ppm group of male rats. In female rats, relative organ weight of the left kidney and the both lungs in 1,620 ppm group and the left lung and the both kidneys in 7,300 ppm group were increased significantly. But the histopathological findings did not reveal any exposure-related changes. According to the above results, the no observable adverse effect level (NOAEL) of isoprene was 7,300 ppm (20.3 mg/L) in both male and female rats. In conclusion, Isoprene was not classified specific target organ toxicity of the 'Standard for Classification and Labeling of Chemical Substance and Material Safety Data Sheet' (Ministry of Employment and Labor, 2009).

A Study on the $NO_2$ Gas Detection Chracteristics of the Octa(2-ethylhexyloxy) Copper-Phthalocyanine LB Film Depending on the Film Thickness and Temperature (두께와 온도에 따른 Octa(2-ethylhexyloxy) Copper-phthalocyanine LB막의 $NO_2$ 가스 탐지 특성에 관한 연구)

  • Yim, Jun-Seok;Shin, Hyun-Man;Kim, Young-Kwan;Kim, Jung-Soo;Sohn, Byung-Chung
    • Journal of the Korean Applied Science and Technology
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    • v.13 no.3
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    • pp.105-109
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    • 1996
  • It is well known that the metallo- phthalocyanine (MPcs) are sensitive to toxic gaseous molecules such as $NO_2$ and also chemically and thermally stable, Therefore, lots of MPcs have been studied for the potential chemical sensor for $NO_2$ gas using quartz crystal microbalance(QCM) or electrical conductivity. In this study, ultra-thin films of octa(2-ethylhexyloxy)copper-phthalocyanine were prepared by Langmuir-Blodgett method and characterized by using UV-VIS absortion spectroscopy and ellipsometry. Transfer condition, and characterization of LB films were investigated and preliminary results of current-voltage(I-V) characteristics of these films exposed to $NO_2$ gas as a function of film thickness and temperature were discussed.

Preparation of CdS-pillared $H_4Nb_6O_7$ and Photochemical Reduction of Nitrate under Visible Light Irradiation

  • Tawkaew, Sittinun;Fujishiro, Yoshinobu;Uchida, Satoshi;Sato, Tsugio
    • The Korean Journal of Ceramics
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    • v.6 no.1
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    • pp.43-46
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    • 2000
  • $H_4Nb_6/O_{17}$/CdS nanocomposites which intercalated CdS particles, less than 0.8nm thickness, in the interlayer of $H_4Nb_6/O_{17}$ were prepared by the successive ion exchange reactions of $H_4Nb_6/O_{17}$ with $Cd^{2+}$ and $C_3H_7NH_3_+$, followed by the reaction with $H_2S$ gas. $H_4Nb_6/O_{17}$/CdS photocatalytically reduced $NO_3$ ̄ to $NO_2$ ̄ and $NH_3$in the presence of sacrificial hole acceptor such as methanol under visible light irradiation (wavelength>400nm), although unsupported CdS showed no noticeable photocatalytic activity for $NO_3$ ̄ reduction. The catalytic activity of $H_4Nb_6/O_{17}$/CdS greatly enhanced with co-doping of Pt particles in the interlayer.

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