• Title/Summary/Keyword: Photolysis

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Photochemistry of 1-(o-Hydroxyphenyl)-2-pentamethyldisilanylethyne : Photoreaction in a Concentrated Benzene Solution and Photoreaction with Methanol or Acetone

  • Park, Seong Gi
    • Bulletin of the Korean Chemical Society
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    • v.22 no.11
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    • pp.1202-1206
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    • 2001
  • Irradiation of 1-(o-hydroxyphenyl)-2-pentamethyldisilanylethyne 1 in a concentrated benzene solution has provided photodimer product 7 along with other reported photoproducts. Irradiation of 1 in methanol yields 1-(o-hydroxyphenyl)-2-trimethylsilylethyne 2 and its reduction product 13, via silacyclopropene intermediate 10, and the reduction product 8 and two methanol addition products, 11 and 12, via o-hydroxyphenylethyne. Photolysis of 1 with acetone in deaerated methylene chloride affords site specific and regioselective 1 : 1 adduct 16 via silacyclopropene intermediate 10.

Photosensitization of Trichlorobenzenes(TCBs) in Aqueous Solution: III. Photoproducts with Nitrite ($\textrm{NO}_2$) and Triethylamine(TEA)

  • Kim, Jae H.
    • Environmental Analysis Health and Toxicology
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    • v.11 no.3_4
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    • pp.33-44
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    • 1996
  • Photolysis of TCBs in aqueous solutions of sodium nitrite and triethylamine (TEA) at neutral pH has been investigated. TCBs yielded trichloronitrobenzenes(TCNBs) as primary photoproducts, and their corresponding trichlorophenols (TCPs) via two types of reaction, one, nitration, and the other, by direct hydroxylation with OH radical. Isomerized products and TCBs were also identified. Photosensitization with TEA resulted in the formation of small yields of dichlorobenzenes(DCBs) by reductive dechlorination of TCBs.

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Surface and Photolytic Characteristics of Ni-TiO2 Composite Layer Electro-Plated from Non-Aqueous Electrolyte (비수용액 전해질에서 전기도금한 니켈-TiO2 복합 도금층의 표면 및 광분해 특성 연구)

  • Jo, Il-Guk;Ji, Chang-Wook;Choi, Chul-Young;Kim, Young-Seok;Kim, Yang-Do
    • Journal of the Korean institute of surface engineering
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    • v.41 no.5
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    • pp.240-244
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    • 2008
  • Composite plating is a method of co-deposition of plating layer with metallic and/or non-metallic particles to improve the plating layer properties such as high corrosion resistance and photolysis of organic compounds. The properties of nickel-ceramic composite plating are significantly depend on the surface characteristics of co-deposited particles as well as the quantity in electrolyte. In this study, Ni-$TiO_2$ composite coating layer was produced by electrodeposition technique from non-aqueous eletrolyte and its surface characteristics as well as photolytic properties were investigated. The amounts of immobilized $TiO_2$ particles increased with increasing the initial $TiO_2$ particles contents in the bath. Samples electroplated with the current density of $0.5\;A/dm^2$ showed the significantly improved homogeneous $TiO_2$ particles distribution. The corrosion resistance of Ni-$TiO_2$ composite coating layer also improved with increaing the amounts of $TiO_2$ particles. Etched sample showed about 10% increased photolytic rate of organic matter compare to that of the non-etched.

Time Resolved Electron Spin Resonance Spectroscopy of Anthrasemiquinone Radical Produced by Pulse Laser Photolysis. A Study on Chemically Induced Dynamic Electron Polarization (광화학 반응에서 생성된 Anthrasemiquinone Radical의 시간분해 ESR ; CIDEP에 관한 연구)

  • Hong Daeil;Kuwata Keiji
    • Journal of the Korean Chemical Society
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    • v.34 no.5
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    • pp.404-412
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    • 1990
  • The time resolved electron spin resonance spectroscopy are used to two measurement methods of chemically induced dynamic electron polarization (CIDEP) and absorption ESR. The spectra of the semiquinone radical anion were successively detected in the laser flash photolysis of anthraquinone in the mixtures of 2-propanol and triethylamine. The semiquinone radical anion was fairly stable and its cw ESR could be observed. The rate constant (T1$^{-1}$) of the spin-depolarization of polarized semiquinone radical anion was 2.6 ${\times}\;1-^5$ sec$^{-1}$ and the decay of the radical anion was the first order with the rate constant (K$_1}$) of 300.0 sec$^{-1}$. The intensity of CIDEP spectra increased with the increasing the microwave power, but the Torrey wiggles appeared following with decay curves.

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Detection and Determination of the Peroxyl Radical in the Photolysis with TiO2 (TiO2와의 광반응하에서 생성되는 페록시라디칼(HO2・/O2-)의 검출 및 정량화)

  • Kwon, Bumgeun;Kim, Jongoh
    • Journal of the Korean GEO-environmental Society
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    • v.11 no.7
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    • pp.45-49
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    • 2010
  • We have developed and demonstrated the use of a new kinetic method as an analytical tool for the measurement of $HO_2{\cdot}/O_2{\cdot}^-$. This new method is based on the reduction of $Fe^{3+}$-Ethylene Diamine Tetra Acetate, EDTA) into $Fe^{2+}$-EDTA by $HO_2{\cdot}/O_2{\cdot}^-$ and the well-known Fenton-like reaction of $H_2O_2$ and $Fe^{2+}$-EDTA to yield the hydroxyl radicals ($OH{\cdot}$). Since this method for $HO_2{\cdot}/O_2{\cdot}^-$ shows high sensitivity and allows a simple calibration system, it can contribute significantly to understanding the basic functions of $HO_2{\cdot}/O_2{\cdot}^-$ in advanced oxidation processes for water treatment. Moreover, the present technique has the advantage of using inexpensive and easily available nonenzymatic reagents and of being insensitive to the moderate concentration of possible interferences often found in aqueous phase.

Improved Photolysis of Water from Ti Incorporated Double Perovskite Sr2FeNbO6 Lattice

  • Borse, P.H.;Cho, C.R.;Yu, S.M.;Yoon, J.H.;Hong, T.E.;Bae, J.S.;Jeong, E.D.;Kim, H.G.
    • Bulletin of the Korean Chemical Society
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    • v.33 no.10
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    • pp.3407-3412
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    • 2012
  • The Ti incorporation at Fe-site in the double perovskite lattice of $Sr_2FeNbO_6$ (SFNO) system is studied. The Ti concentration optimization yielded an efficient photocatalyst. At an optimum composition of Ti as x = 0.07 in $Sr_2Fe_{1-x}Ti_xNbO_6$, the photocatalyst exhibited 2 times the quantum yield for photolysis of $H_2O$ in presence of $CH_3OH$, than its undoped counterpart under visible light (${\lambda}{\geq}420nm$). Heavily Ti-doped $Sr_2Fe_{1-x}Ti_xNbO_6$ lattice exhibited poor photochemical properties due to the existence of constituent impurity phases as observed in the structural characterization, as well as deteriorated optical absorption. The higher electron-density acquired by n-type doping seem to be responsible for the more efficient charge separation in $Sr_2Fe_{1-x}Ti_xNbO_6$ (0.05 < x < 0.4) and thus consequently displays higher photocatalytic activity. The Ti incorporated structure also found to yield stable photocatalyst.

The Solvent Effect on the Chemical Changes in Binary Mixture : i.e. THF-H2O System (Ⅰ) (이성분 혼합용매에서 화학변화에 미치는 용매의 영향 : THF-$H_2O$ (제1보). 용매화된 전자의 흡수스펙트럼)

  • Yu-Chul Park;Sang Oh;P. Krebs;U. Schindewolf
    • Journal of the Korean Chemical Society
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    • v.24 no.5
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    • pp.371-379
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    • 1980
  • The spectral properties of the solvated electrons in tetrahydrofuran(THF)-water binary system have been investigated. In this study, the solvated electrons have been produced by applying nsec Q-switch Nd(YAG) laser photolysis technique. The experimental method photolysis were schematically described. The solvent and the temperature effects on the absorption spectrum of solvated electrons have also been studied. The observation of the spectrum with increasing THF content and temperatue showed a trend that the former shifted to longer wavelength and the other showed broadening effect. The half-life of solvated electrons were also increased with THF content. The absorption maxima of the mixtures were always observed in the middle of that of pure water and THF. The correlation between the volume and the absorption energy of solvated electrons were discussed from the results.

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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.

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.

Photochemical Reductions of Benzil and Benzoin in the Presence of Triethylamine and TiO? Photocatalyst

  • Park, Joon-Woo;Kim, Eun-Kyung;Koh Park, Kwang-Hee
    • Bulletin of the Korean Chemical Society
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    • v.23 no.9
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    • pp.1229-1258
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    • 2002
  • This paper reports the photochemical reduction of benzil 1 to benzoin 2 and the reduction of 2 to hydrobenzoin 4 in deoxygenated solvents in the presence of triethylamine (TEA) and/or TiO2. Without TEA or TiO2, the photolysis of 1 resulted in very low yield of 2. The presence of TEA or TiO2 increased the rate of disappearance of 1 and the yield of 2, which were further increased considerably by the presence of water. The photoreduction of 1 to 2 proceeds through an electron transfer to 1 from TEA or hole-scavenged excited TiO2 followed by protonation. In the reaction medium of 88 : 7 : 2 : 3 CH3CN/CH3OH/H2O/TEA with 2.5 $㎎/m{\ell}$ of TiO2, the yield of 2 was as high as 85 % at 50 % conversion of 1. The photolysis of 2 in homogeneous media resulted in photo-cleavage to benzoyl and hydroxybenzyl radicals, which are mostly converted to benzaldehyde. The reduction product 4 is formed in low yield through the dimerization of hydroxybenzyl radicals. The addition of TEA increased the conversion rate of 2 and the yield of 4 significantly. This was attributed to the scavenging effect of TEA for benzoyl radical to produce N,N-diethylbenzamide and the photoreduction of benzaldehyde in the presence of TEA. The ratio of $(\pm)$ and meso isomers of 4 obtained from the photochemical reaction is about 1.1. This ratio is the same as that from the photochemical reduction of benzaldehyde in the presence of TEA. In the TiO2-sensitized photochemical reduction of 2, meso-4 was obtained in moderate yield. The reduction of 2 to 4 proceeds through two consecutive electron/proton transfer processes on the surface of the photocatalyst without involvement of ${\alpha}-cleavage$. The radical 11 initially formed from 2 by one electron/proton process can also combine with hydroxy methyl radical, which is generated after hole trapping of excited TiO2 by methanol, to produce 1,2-diphenylpropenone after dehydration reaction.