• Title/Summary/Keyword: adsorption/catalysis effect

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Preparation and Pore-Characteristics Control of Nano-Porous Materials using Organometallic Building Blocks

  • Oh, Gyu-Hwan;Park, Chong-Rae
    • Carbon letters
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    • v.4 no.1
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    • pp.1-9
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    • 2003
  • Recently, the control of pore-characteristics of nano-porous materials has been studied extensively because of their unique applications, which includes size-selective separation, gas adsorption/storage, heterogeneous catalysis, etc. The most widely adopted techniques for controlling pore characteristics include the utilization of pillar effect by metal oxide and of templates such as zeolites. More recently, coordination polymers constructed by transition metal ions and bridging organic ligands have afforded new types of nano-porous materials, porous metal-organic framework(porous MOF), with high degree and uniformity of porosity. The pore characteristics of these porous MOFs can be designed by controlling the coordination number and geometry of selected metal, e.g transition metal and rare-earth metal, and the size, rigidity, and coordination site of ligand. The synthesis of porous MOF by the assembly of metal ions with di-, tri-, and poly-topic N-bound organic linkers such as 4,4'-bipyridine(BPY) or multidentate linkers such as carboxylates, which allow for the formation of more rigid frameworks due to their ability to aggregate metal ions into M-O-C cluster, have been reported. Other porous MOF from co-ligand system or the ligand with both C-O and C-N type linkage can afford to control the shape and size of pores. Furthermore, for the rigidity and thermal stability of porous MOF, ring-type ligand such as porphyrin derivatives and ligands with ability of secondary bonding such as hydrogen and ionic bonding have been studied.

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Effect of the Structure of MoO3/bismuth molybdate Binary Phase Catalysts on the Selective Oxidation of Propylene (MoO3/bismuth molybdate 혼합 2상 촉매의 구조에 따른 프로필렌 선택산화반응 특성)

  • Cha, T.B.;Choi, M.J.;Park, D.W.;Chung, J.S.
    • Applied Chemistry for Engineering
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    • v.3 no.1
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    • pp.53-63
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    • 1992
  • M/BM -series catalysts, $MoO_3$ supported on ${\alpha}-Bi_2Mo_3O_{12}$ were also prepared by impregnation method. BM/M-series catalysts, ${\alpha}-Bi_2Mo_3O_{12}$ supported on $MoO_3$ were also prepared by coprecipitation. Structure and catalytic properties of the two phase catalysts were studied by means of using nitrogen adsorption, X-ray diffraction, and scanning electron microscopy. The reaction test for the selective oxidation of propylene to acrolein over Bi-molybdate catalysts was studied using a fixed-bed reactor system. In M/BM-series catalysts, $MoO_3$ was dispersed on ${\alpha}-Bi_2Mo_3O_{12}$, and the crystal structure of ${\alpha}-Bi_2Mo_3O_{12}$ remains unchanged by the presence of excess $MoO_3$. However the surface morphology and bulk structure of BM/M-series catalysts were altered probably because the precipitated $Bi(OH)_3$ reacted with $MoO_3$ during the calcination to form ${\alpha}-Bi_2Mo_3O_{12}$ phase. The results of propylene oxidation on both series catalysts showed that the reaction took place over the surface of ${\alpha}-Bi_2Mo_3O_{12}$ particle and the role of excess $MoO_3$ was to supply oxygen to ${\alpha}-Bi_2Mo_3O_{12}$. These increasing effects on activity were also observed in the mechanical mixtures of ${\alpha}-Bi_2Mo_3O_{12}$ and $MoO_3$.

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Continuous Wet Oxidation of TCE over Supported Metal Oxide Catalysts (금속산화물 담지촉매상에서 연속 습식 TCE 분해반응)

  • Kim, Moon Hyeon;Choo, Kwang-Ho
    • Korean Chemical Engineering Research
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    • v.43 no.2
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    • pp.206-214
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    • 2005
  • Heterogeneously-catalyzed oxidation of aqueous phase trichloroethylene (TCE) over supported metal oxides has been conducted to establish an approach to eliminate ppm levels of organic compounds in water. A continuous flow reactor system was designed to effect predominant reaction parameters in determining catalytic activity of the catalysts for wet TCE decomposition as a model reaction. 5 wt.% $CoO_x/TiO_2$ catalyst exhibited a transient period in activity vs. on-stream time behavior, suggesting that the surface structure of the $CoO_x$ might be altered with on-stream hours; regardless, it is probable to be the most promising catalyst. Not only could the bare support be inactive for the wet decomposition reaction at $36^{\circ}C$, but no TCE removal also occurred by the process of adsorption on $TiO_2$ surface. The catalytic activity was independent of all particle sizes used, thereby representing no mass transfer limitation in intraparticle diffusion. Very low TCE conversion appeared for $TiO_2$-supported $NiO_x$ and $CrO_x$ catalysts. Wet oxidation performance of supported Cu and Fe catalysts, obtained through an incipient wetness and ion exchange technique, was dependent primarily on the kinds of the metal oxides, in addition to the acidic solid supports and the preparation routes. 5 wt.% $FeO_x/TiO_2$ catalyst gave no activity in the oxidation reaction at $36^{\circ}C$, while 1.2 wt.% Fe-MFI was active for the wet decomposition depending on time on-stream. The noticeable difference in activity of the both catalysts suggests that the Fe oxidation states involved to catalytic redox cycle during the course of reaction play a significant role in catalyzing the wet decomposition as well as in maintaining the time on-stream activity. Based on the results of different $CoO_x$ loadings and reaction temperatures for the decomposition reaction at $36^{\circ}C$ with $CoO_x/TiO_2$, the catalyst possessed an optimal $CoO_x$ amount at which higher reaction temperatures facilitated the catalytic TCE conversion. Small amounts of the active ingredient could be dissolved by acidic leaching but such a process gave no appreciable activity loss of the $CoO_x$ catalyst.