• Title/Summary/Keyword: Gas-phase photolysis

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High-Yield Gas-Phase Laser Photolysis Synthesis of Germanium Nanocrystals for High-Performance Lithium Ion Batteries (고성능 리튬이온 전지를 위한 저마늄 나노입자의 가스상 레이저 광분해 대량 합성법 개발)

  • Kim, Cang-Hyun;Im, Hyung-Soon;Cho, Yong-Jae;Chung, Chan-Su;Jang, Dong-Myung;Myung, Yoon;Kim, Han-Sung;Back, Seung-Hyuk;Im, Young-Rok;Park, Jeung-Hee;Song, Min-Seob;Cho, Won-Il;Cha, Eun-Hee
    • Journal of the Korean Electrochemical Society
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    • v.15 no.3
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    • pp.181-189
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    • 2012
  • We developed a new high-yield synthesis method of free-standing germanium nanocrystals (Ge NCs) by means of the gas-phase photolysis of tetramethyl germanium in a closed reactor using an Nd-YAG pulsed laser. Size control (5-100 nm) can be simply achieved using a quenching gas. The $Ge_{1-x}Si_x$ NCs were synthesized by the photolysis of a tetramethyl silicon gas mixture and their composition was controlled by the partial pressure of precursors. The as-grown NCs are sheathed with thin (1-2 nm) carbon layers, and well dispersed to form a stable colloidal solution. Both Ge NC and Ge-RGO hybrids exhibit excellent cycling performance and high capacity of the lithium ion battery (800 and 1100 mAh/g after 50 cycles, respectively) as promising anode materials for the development of high-performance lithium batteries. This novel synthesis method of Ge NCs is expected to contribute to expand their applications in high-performance energy conversion systems.

Depletion Kinetics of the Ground State CrO Generated from the Reaction of Unsaturated Cr(CO)x with O2 and N2O

  • Son, H.S.;Ku, J.K.
    • Bulletin of the Korean Chemical Society
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    • v.23 no.2
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    • pp.184-188
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    • 2002
  • Unsaturated $Cr(CO)_x(1{\leq}x{\leq}5)$molecules were generated in the gas phase from photolysis of $Cr(CO)_6$vapor in He using an unfocussed weak UV laser pulse and their reactions with $O_2$ and $N_2O$ have been studied. The formation and disappearance of the ground state CrO molecules were identified by monitoring laser-induced fluorescence(LIF) intensities vs delay time between the photolysis and probe pulses. The photolysis laser power dependence as well as the delay time dependence of LIF intensities from the CrO orange system showed different behavior as those from ground state Cr atoms, suggesting that the ground state CrO molecules were generated from the reaction between $O_2/N_2O$ and photo-fragments of $Cr(CO)_6$ by one photon absorption. The depletion rate constants for the ground state CrO by $O_2$ and $N_2O$ are $5.4{\pm}0.2{\times}10^{-11}$ and $6.5{\pm}0.4{\times}10^{-12}cm^3molecule^{-1}s^{-1}$, respectively.

A Study on the reaction rate constant by UV Photooxidation and Photo-catalytic oxidation process (광산화 및 광촉매 공정에서 VOCs의 산화반응 속도 산출에 관한 연구)

  • Jeong, Chang Hun;Lee, Gyeong Ho
    • Journal of Environmental Science International
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    • v.13 no.1
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    • pp.37-40
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    • 2004
  • In this study, the decomposition of gas-phase TCE, Benzene and Toluene, in air streams by direct UV Photolysis and UV/TiO$_2$ process was studied. For direct UV Photolysis, by regressing with computer calculation to the experimental results the value of reaction rate constant k of TCE, Toluene and Benzene in this work were determined to be 0.00392s$\^$-l/, 0.00230s$\^$-1/ and 0.00126s$\^$-1/, respectively. And the adsorption constant K of TCE, Toluene and Benzene in this work were determined to be 0.0519 mol$\^$-l/ ,0.0313mo1$\^$-1/ and 0.0084mo1$\^$-1/, respectively. For UV/TiO$_2$ system by regressing with computer calculation to the experimental results the value of reaction rate constant k of TCE, Toluene, and Benzene in this work were determined to be 5.74g/$\ell$$.$min, 3.85g/$\ell$$.$min, and 1.18g/$\ell$$.$min, respectively. And the catalyst adsorption constant K of TCE, Toluene, and Benzene in this work were determined to be 0.0005㎥/mg, 0.0043㎥/mg and 0.0048㎥/mg, respectively.

A Study on the removal of B.T.X by UV Photooxidation-Activated Carbon (광산화-활성탄 복합공정에 의한 B.T.X. 분해에 관한 연구)

  • Jeong, Chang Hun;Bae, Hae Ryong
    • Journal of Environmental Science International
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    • v.13 no.1
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    • pp.41-45
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    • 2004
  • In this study, The decomposition of gas-phase Benzene and Toluene, Xylene in air streams by direct UV Photolysis, UV/TiO$_2$ and UV/TiO$_2$/A.C process was studied. The experiments were carried out under various UV light intensities and initial concentrations of B.T.X to investigate and compare the removal efficiency of the pollutant. B.T.X was determined by GC-FID of gas samples taken from the a glass sampling bulb which was located at reactor inlet and outlet by gas-tight syringe. From this study, the results indicate that UV/TiO$_2$/A.C system (photooxidation-photocatalytic oxidation-adsorption process) is ideal for treatment of B.T.X from the small workplace. Although the results needs more verifications, the methodology seems to be reasonable and can be applied for various workplace (laundry, gas station et al.).

Tin Germanium Sulfide Nanoparticles for Enhanced Performance Lithium Secondary Batteries (고성능 리튬 이차 전지를 위한 황화 주석 저마늄 (SnxGe1-xS) 나노입자 연구)

  • Cha, E.H.;Kim, Y.W.;Lim, S.A.;Lim, J.W.
    • Journal of the Korean Electrochemical Society
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    • v.18 no.1
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    • pp.31-37
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    • 2015
  • Composition-controlled ternary components chalcogenides germanium tin sulfide ($Sn_xGe_{1-x}S$) nanoparticles were synthesized by a novel gas-phase laser photolysis reaction of tetramethyl germanium, tetramethyl tin, and hydrogen sulfide mixture. Subsequent thermal annealing of as-grown amorphous nanoparticles produced the crystalline orthorhombic phase nanoparticles. All these composition-tuned nanoparticles showed excellent cycling performance of the lithium ion battery. The germanium sulfide nanoparticles exhibit a maximum capacity of 1200 mAh/g after 70 cycles. As the tin composition (x) increases, the capacity maintains better at the higher discharge/charge rate. This novel synthesis method of tin germanium sulfide nanoparticles is expected to contribute to expand their applications in high-performance energy conversion systems.

CRDS Study of Tropospheric Ozone Production Kinetics : Isoprene Oxidation by Hydroxyl Radical

  • Park, Ji-Ho
    • Journal of Environmental Health Sciences
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    • v.35 no.6
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    • pp.532-537
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    • 2009
  • The tropospheric ozone production mechanism for the gas phase additive oxidation reaction of hydroxyl radical (OH) with isoprene (2-methyl-1,3-butadiene) has been studied using cavity ring-down spectroscopy (CRDS) at total pressure of 50 Torr and 298 K. The applicability of CRDS was confirmed by monitoring the shorter (~4%) ringdown time in the presence of hydroxyl radical than the ring-down time without the photolysis of hydrogen peroxide. The reaction rate constant, $(9.8{\pm}0.1){\times}10^{-11}molecule^{-1}cm^3s^{-1}$, for the addition of OH to isoprene is in good agreement with previous studies. In the presence of $O_2$ and NO, hydroxyl radical cycling has been monitored and the simulation using the recommended elementary reaction rate constants as the basis to OH cycling curve gives reasonable fit to the data.

Reaction of Cr Atoms with O2 at Low Pressures: Observation of New Chemiluminescence Bands from CrO2*

  • Son, Hyung-Su;Ku, Ja-Kang
    • Bulletin of the Korean Chemical Society
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    • v.25 no.2
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    • pp.226-232
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    • 2004
  • Ground and low-lying electronic states of Cr atoms in the gas phase were generated from photolysis of $Cr(CO)_6$ vapor in He or Ar using an unfocussed weak UV laser pulse and their reactions with $O_2$ and $N_2O$ were studied. When 0.5-1.0 Torr of $Cr(CO)_6$ /$O_2$ /He or Ar mixtures were photolyzed using 295-300 nm laser pulses, broadband chemiluminescence peaked at ~420 and ~500 nm, respectively, was observed in addition to the atomic emissions from $z^7P^{\circ}$, $z^5P^{\circ}$, and $y^7P^{\circ}$ states of Cr atoms. When $N_2O$ was used instead of $O_2$, no chemiluminescence was observed. The chemiluminescence intensities as well as the LIF intensities for those three low-lying electronic states ($a^7S_3,\;a^5S_2\;and\;a^5D_J$) showed second-order dependence on the photolysis laser power. Also, the chemiluminescence intensities were first-order in $O_2$ pressure, but the presence of excess Ar showed a strong inhibition effect on them. Based on the experimental results, the chemiluminecent species in this work is attributed to $CrO_2^*$ generated from hot ground state Cr atoms with $O_2$. The apparent radiative lifetimes of the chemiluminescent species and collisional quenching rate constants by $O_2$ and Ar also were investigated.

A Gas-Phase Investigation of Oxygen-Hydrogen Exchange Reaction of O(3P) + C2H5 → H(2S) + C2H4O

  • Jang, Su-Chan;Park, Min-Jin;Choi, Jong-Ho
    • Bulletin of the Korean Chemical Society
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    • v.35 no.3
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    • pp.839-844
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    • 2014
  • The gas-phase radical-radical reaction $O(^3P)$ + $C_2H_5$ (ethyl) ${\rightarrow}$ $H(^2S)$ + $CH_3CHO$(acetaldehyde) was investigated by applying a combination of vacuum-ultraviolet laser-induced fluorescence spectroscopy in a crossed beam configuration and ab initio calculations. The two radical reactants $O(^3P)$ and $C_2H_5$ were respectively produced by photolysis of $NO_2$ and supersonic flash pyrolysis of the synthesized precursor azoethane. Doppler profile analysis of the nascent H-atom products in the Lyman-${\alpha}$ region revealed that the average translational energy of the products and the average fraction of the total available energy released as translational energy were $5.01{\pm}0.72kcalmol^{-1}$ and 6.1%, respectively. The empirical data combined with CBS-QB3 level ab initio theory and statistical calculations demonstrated that the title exchange reaction is a major channel and proceeds via an addition-elimination mechanism through the formation of a short-lived, dynamical addition complex on the doublet potential energy surface. On the basis of systematic comparison with several exchange reactions of hydrocarbon radicals, the observed small kinetic energy release can be explained in terms of the loose transition state with a product-like geometry and a small reverse activation barrier along the reaction coordinate.