• 제목/요약/키워드: photolysis

검색결과 236건 처리시간 0.037초

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

  • 박성기
    • Bulletin of the Korean Chemical Society
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    • 제22권11호
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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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    • 제11권3_4호
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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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비수용액 전해질에서 전기도금한 니켈-TiO2 복합 도금층의 표면 및 광분해 특성 연구 (Surface and Photolytic Characteristics of Ni-TiO2 Composite Layer Electro-Plated from Non-Aqueous Electrolyte)

  • 조일국;지창욱;최철영;김영석;김양도
    • 한국표면공학회지
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    • 제41권5호
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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.

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

  • 홍대일
    • 대한화학회지
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    • 제34권5호
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    • pp.404-412
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    • 1990
  • 시간분해 ESR 분광법에서는 CIDEP법과 흡수 ESR 분광법을 사용하였다. 2-프로판올과 트리에틸아민 혼합용매에서 anthraquinone이 레이저 광선에 의해서 생성된 anthraquinone 라디칼 음이온을 시간분해 ESR 분광법으로 측정하였다. 이 semiquinone 라디칼은 대단히 안정하여 cw ESR을 측정할 수 있었다. 분극된 semiquinone 라디칼이 열적 평형상태로 소멸되는 속도상수는 스핀-격자 완화시간의 역수로서 2.6 ${\times}\;1-^5$ sec$^{-1}$이다. 그리고, 그 라디칼의 소멸속도상수는 300.0 sec$^{-1}$이다. CIDEP스펙트럼의 시간의존성에 대한 강도 변화는 마이크로파 출력이 강할수록 일반적으로 증가하였다. 그러나, 지나치게 출력을 높이면 감소 곡선상에 Torrey 진동이 뒷따라 일어났다.

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

  • 권범근;김종오
    • 한국지반환경공학회 논문집
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    • 제11권7호
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    • pp.45-49
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    • 2010
  • 본 연구는 수중에서 광분해 반응시 발생되는 페록시라디칼을 검출하고 정량화하는 방법에 관한 것으로 비교적 간단한 방법으로 높은 감응도를 나타낼 수 있어 수처리를 위한 고도산화공정에서 유기물 분해를 위해 주요 역할을 하는 페록시라디칼의 정량화에 효과적으로 이용될 수 있다. 이 방법은 페록시라디칼이 $Fe^{3+}$-EDTA와 반응하여 $Fe^{2+}$-EDTA로 환원되는 반응에 기초를 둔 것으로 경제적이며 검출 및 정량을 위해서 손쉽게 사용할 수 있는 비효소계의 시약을 사용한다는 이점과 수계에서 흔히 발생하는 반응의 방해에 민감하지 않은 장점을 지니고 있다.

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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    • 제33권10호
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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.

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

  • 박유철;오상천
    • 대한화학회지
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    • 제24권5호
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    • pp.371-379
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    • 1980
  • 테트라히드로퓨란(THF)-물 혼합용매에서 용매화된 전자($e^-_s$)를 생성시켜 광흡수스펙트럼의 성질을 연구하였다. 본 연구에서 $e^-_s$는 nsec Q 스위치 Nd(YAG) 레이저 에너지 (265nm)를 이용한 광분해법으로 생성시켰다. 이 방법은 실험부분에서 도면으로 간단하게 기술되어 있다. 측정한 $e^-_s$의 최대흡수 파장은 THF의 함량과 온도에 따라 장파장쪽으로 이동하였고, 흡수스펙트럼의 폭 역시 THF에 따라 증가하였다. $e^-_s$의 반감기 또한 THF의 몰%에 따라 증가하였다. 혼합용매에서 최대 흡수파장은 순수한 물이나 THF에서 방사선 분해법을 측정한 흡수파장의 중간에서 모두 발견되었다. 이러한 실험 결과로부터 $e^-_s$의 체적과 최대흡수에너지 관계를 논의할 수 있었다.

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

  • 차은희;김영운;임수아;임재욱
    • 전기화학회지
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    • 제18권1호
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    • pp.31-37
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    • 2015
  • 삼성분 칼코게나이드 화합물인 황화 주석 저마늄 ($Sn_xGe_{1-x}S$) 합금 나노입자를 메틸 주석 $(Sn(CH_3)_4$, tetramethyl tin, TMT) 메틸 저마늄 $(Ge(CH_3)_4$, tetramethyl germanium, TMG), 황화수소 ($H_2S$, hydrogen sulfide) 혼합 가스의 레이저 광분해 반응법으로 합성할 수 있으며, 이때 반응기 안의 가스 혼합비율에 따라 나노입자의 주석과 저마늄의 조성비를 조절할 수 있었다. 조성비를 가변시킨 나노입자는 모두 결정성을 갖게 만들 수 있었으며, 리튬 이온 전지의 음극소재로서 우수한 특성을 보여주었다. 조성비에 따라 특성을 조사결과, 황화저마늄은 70 사이클 후 최대 1200 mAh/g의 가장 높은 방전용량을 갖는 것과, 주석 성분 함량이 클수록 높은 충방전률에서 용량 유지가 더 잘 됨을 확인하였다. 이와 같은 우수한 효율의 황화물 합금 나노입자의 새로운 대량 합성법은 고성능 에너지 변환 소재 실용화에 기여할 것으로 예상된다.

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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    • 제25권2호
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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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    • 제23권9호
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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.