• 제목/요약/키워드: Catalytic mechanism

검색결과 312건 처리시간 0.024초

NiO 촉매에 의한 CO 산화반응에 관한 연구 (A Study on the Catalytic Oxidation Reaction of Carbon Monoxide with Nickel Oxide)

  • 최재시;김규홍
    • 대한화학회지
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    • 제13권4호
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    • pp.241-247
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    • 1969
  • The catalytic reaction between carbon monoxide and oxygen was investigated with the various nickel oxide catalysts at different partial pressures of carbon monoxide and oxygen and at reaction temperatures in the region of 120$^{circ}$to 250$^{circ}C$. The reaction has the highest rate with the nickel oxide catalyst which is sintered at low temperature. A reaction mechanism to explain the data is derived. From the Arrhenius equation, the activation energies in the region of experimental temperatures are found to be from 5.49 to 9.15 kcal/mole. The concentration of excess oxygen in the nickel oxide seems to vary according to the sintering temperatures and periods and is the controlling factor in determining the type of kinetics followed by the catalytic reaction.

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The Oxidation of Hydrazobenzene Catalyzed by Cobalt Complexes in Nonaqueous Solvents

  • Kim, Stephen S.B.;Hommer, Roger B.;Cannon, Roderick D.
    • Bulletin of the Korean Chemical Society
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    • 제27권2호
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    • pp.255-265
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    • 2006
  • The oxidation of hydrazobenzene by molecular oxygen in the polar solvent methanol is catalysed by a Schiff's base complex Co(3MeOsalen) which is a synthetic oxygen carrier. The products are trans-azobenzene and water. The rate of the reaction has been studied spectrophotometrically and the rate law established. A mechanism involving a ternary complex of catalyst, hydrazobenzene and molecular oxygen has been proposed. The kinetic studies show that a ternary complex $CoL{\cdot}H_2AB{\cdot}O_2$ is involved in the rate determining step. The reactions are summarised in a catalytic cycle. The kinetic data suggest that a ternary complex involving Co(3MeOsalen), triphenyl-phosphine and molecular oxygen is catalytically acive species but at higher triphenylphosphine concentrations the catalyst becomes inactive. The destruction of the catalytic activity could be due to the catalyst becoming coordinated with triphenyl phosphine at both z axis sites of the complex e.g. Co (3MeOsalen)$(PPh_3)_2$.

PARTIAL OXIDATION OF PROPANE ON NAFION SUPPORTED CATALYTIC MEMBRANE

  • F. Frusteri;C. Espro;F. Arena;F. Arena;E. Passalacqua;A.Patti;A. Parmaliana
    • 한국막학회:학술대회논문집
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    • 한국막학회 1999년도 The 7th Summer Workshop of the Membrane Society of Korea
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    • pp.55-58
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    • 1999
  • Nafion supported catalytic membranes were found to be active, stable and selective in th partial oxidation of propane to oxygenates with H2O2 under mild condition. Addition of Fe2+ in liquid phase enhances the reaction rate. Reaction proceeds according to a radical mechanism based on th electrophilic activation of propane on superacid sites and subsequent reaction of the activated paraffin with OH radicals. The use of a catalytic membrane, which allow separation of the intermediate products from the liquid phase containing the oxidant, was found to be effective to perform selective partial oxidation of propane with high yields to oxygenated products.

Self-catalytic Growth of ${\beta}$-Ga2O3 Nanowires Deposited by Radio-Frequency Magnetron Sputtering

  • 최광현;강현철
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
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    • pp.291.2-291.2
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    • 2013
  • Growth behavior of b-Ga2O3 nanowires (NWs) on sapphire(0001) substrates during radio-frequency magnetron sputtering is reported. Upon fabrication, flat thin films grew initially, subsequent to which, NW bundles were formed on the surface of thin film with increasing film thickness. This transition of the growth mode occurred only at temperatures greater than ${\sim}450^{\circ}C$. The b-Ga2O3 NWs were grown through the self-catalytic vapor-liquid-solid mechanism with self-assembled Ga seeds. Secondary growth of NWs, which occurred from the sides of primary NWs resulting in branched NW structures, was also observed. Finally, the room temperature photoluminescence properties of as-grown and annealed b-Ga2O3 NW samples were investigated.

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Catalytic effect of metal oxides on CO2 absorption in an aqueous potassium salt of lysine

  • Dharmalingam, Sivanesan;Park, Ki Tae;Lee, Ju-Yeol;Park, Il-Gun;Jeong, Soon Kwan
    • Journal of Industrial and Engineering Chemistry
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    • 제68권
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    • pp.335-341
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    • 2018
  • We report the catalytic effects of metal oxides on the $CO_2$ absorption rate in an aqueous potassium salt of ${\text\tiny{L}}-lysine-HCl$ using the vapor liquid equilibrium method. The best $CO_2$ absorption rate obtained through testing metal oxides in a highly concentrated potassium salt of amino acids (2.0 M) was identified using CuO. The recyclability of the metal oxides was tested over three cycles. The catalyst CuO was found to enhance the absorption rate of $CO_2$ by 61%. A possible mechanism was proposed based on NMR spectroscopy studies. Further, the effect of change in liquid absorbent viscosity on $CO_2$ absorption is discussed.

A Study on the Sulfur-Resistant Catalysts for Water Gas Shift Reaction III. Modification of $Mo/γ-Al_2O_3$ Catalyst with Iron Group Metals

  • 박진남;김재현;이호인
    • Bulletin of the Korean Chemical Society
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    • 제21권12호
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    • pp.1233-1238
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    • 2000
  • $Mo/{\gamma}-Al_2O_3catalysts$ modified with Fe, Co, and Ni were prepared by impregnation method and catalytic activity for water gas shift reaction was examined. The optimum amount of Mo loaded for the reaction was 10 wt% $MoO_3$ to ${\gamma}-Al_2O_3.$ The catalytic activity of $MoO_3/{\gamma}-Al_2O_3was$ increased by modifying with Fe, Co, and Ni in the order of Co${\thickapprox}$ Ni > Fe. The optimum amounts of Co and Ni added were 3 wt% based on CoO and NiO to 10 wt% $MoO_3/{\gamma}-Al_2O_3$, restectively. The TPR (temperature-programmed reduction) analysis revealed that the addition of Co and Ni enganced the reducibility of the catalysts. The results of both catalytic activity and TPR experiments strongly suggest that the redox property of the catalyst is an important factor in water gas shift reaction on the sulfided Mo catalysts, which could be an evidence of oxy-sulfide redox mechanism.

Rutheniumhydridonitrosyl 착물을 이용한 불포화 유기화합물의 수소화 반응 (Catalytic Hydrogenation of Unsaturated Organic Compounds by Rutheniumhydridonitrosyl Complexes)

  • 박미영;김영중;조욱재;이익모
    • 대한화학회지
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    • 제40권6호
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    • pp.445-452
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    • 1996
  • Hydridonitrosyl complex의 촉매 활용 가능성과 반응 mechanism을 조사하기 위하여 $RuH(NO)(PPh_3)_3$와 RuH(NO)(etp)에 의한 ketone과 aldehyde의 수소화 반응을 연구하였다. 이 촉매들은 ketone과 aldehyde의 수소화 반응에 대하여 촉매 활성을 보이고 있으며, 활성은 기질의 입체장애 및 전자적 요인에 의존하고 있다. 즉, 입체 장애가 적을수록 촉매의 활성이 증가하며, 전자적 요인의 효과는 ketone의 경우 carbonyl carbon의 부분양전하의 양이 증가할수록, aldehyde의 경우는 carbonyl group의 double bond character가 강할수록 반응성이 증대되는 방향으로 나타나고 있다. 이러한 결과는 ketone과 aldehyde의 반응 mechanism이 다름을 반영하고 있다. 한편, RuH(NO)(etp)와 과잉의 $PPh_3$ 존재하에서 $RuH(NO)(PPh_3)_3$가 촉매 활성을 보이고 있음은 NO ligand의 결합방식의 변화를 통한 반응경로가 존재함을 확인하고 있다. 과잉의 $PPh_3$는 촉매와의 몰비가 변함에 따라 작용의 변화(ligand의 해리 방지 ${\rightarrow}$ 염기 ${\rightarrow}$ ligand)가 나타나며 촉매 활성에 영향을 미치고 있다. 이러한 결과를 이해하기 위하여 각 촉매에 대한 반응 mechanism을 제시하였다. 한편, 동일한 기질에 있어서 RuH(NO)(etp)의 활성은 항상 $RuH(NO)(PPh_3)_3$에 비하여 낮았으며 이는 주로 착물의 구조차이에 기인한 것으로 해석되며, 경쟁반응에 있어서는 olefin의 수소화 반응이 carbonyl group의 수소화 반응보다 선택적으로 진행되고 있다.

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Influence of Charge Transport of Pt-CdSe-Pt Nanodumbbells and Pt Nanoparticles/GaN on Catalytic Activity of CO Oxidation

  • Kim, Sun Mi;Lee, Seon Joo;Kim, Seunghyun;Kwon, Sangku;Yee, Kiju;Song, Hyunjoon;Somorjai, Gabor A.;Park, Jeong Young
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2013년도 제44회 동계 정기학술대회 초록집
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    • pp.164-164
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    • 2013
  • Among multicomponent nanostructures, hybrid nanocatalysts consisting of metal nanoparticle-semiconductor junctions offer an interesting platform to study the role of metal-oxide interfaces and hot electron flows in heterogeneous catalysis. In this study, we report that hot carriers generated upon photon absorption significantly impact the catalytic activity of CO oxidation. We found that Pt-CdSe-Pt nanodumbbells exhibited a higher turnover frequency by a factor of two during irradiation by light with energy higher than the bandgap of CdSe, while the turnover rate on bare Pt nanoparticles didn't depend on light irradiation. We also found that Pt nanoparticles deposited on a GaN substrate under light irradiation exhibit changes in catalytic activity of CO oxidation that depends on the type of doping of the GaN. We suppose that hot electrons are generated upon the absorption of photons by the semiconducting nanorods or substrates, whereafter the hot electrons are injected into the Pt nanoparticles, resulting in the change in catalytic activity. We discuss the possible mechanism for how hot carrier flows generated during light irradiation affect the catalytic activity of CO oxidation.

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