• Title/Summary/Keyword: late transition metals

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Oligomerizations and Polymerizations of Olefins by Various Late Transition Metal Catalysts

  • Bahuleyan Bijal Kottukkal;Lee Kyoung-Ju;Son Gi-Wan;Choi Jae-Ho;Chandran Deepak;Abraham Sinoj;Ha Chang-Sik;Kim Il
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.155-155
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    • 2006
  • The most commercially and academically advanced catalysts of late transition metals are diimine complexes based on Pd(II)/Ni(II) and bis(imino)pyridyl complexes based on Fe(II)/Co(II). It is well known that the former systems yield branched polyethylenes and the latter linear PEs. In this presentation, effect of extremely bulky ligands with electron withdrawing/donating substituents at a remote position from Ni(II) metal center and of using multi-nuclear homo or hetero multi-metal on the ethylene polymerization is to be paged.

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Novel solvothermal approach to hydrophilic nanoparticles of late transition elements and its evaluation by nanoparticle tracking analysis

  • Dutilleul, Marion Collart;Seisenbaeva, Gulaim A.;Kessler, Vadim G.
    • Advances in nano research
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    • v.2 no.2
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    • pp.77-88
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    • 2014
  • Solvothermal treatment of late transition metal acetylacetonates in a novel medium composed either of pure acetophenone or acetophenone mixtures with amino alcohols offers a general approach to uniform hydrophilic metal nanoparticles with high crystallinity and low degree of aggregation. Both pure metal and mixed-metal particles can be accesses by this approach. The produced materials have been characterized by SEM-EDS, TEM, FTIR in the solid state and by Nanoparticle Tracking Analysis in solutions. The chemical mechanisms of the reactions producing nanoparticles has been followed by NMR. Carrying out the process in pure acetophenone produces palladium metal, copper metal with minor impurity of $Cu_2O$, and NiO. The synthesis starting from the mixtures of Pd and Ni acetylacetonates with up to 20 mol% of Pd, renders in minor yield the palladium-based metal alloy along with nickel oxide as the major phase. Even the synthesis starting from a mixed solution of $Cu(acac)_2$ and $Ni(acac)_2$ produces oxides as major products. The situation is improved when aminoalcohols such as 2-aminoethanol or 2-dimethylamino propanol are added to the synthesis medium. The particles in this case contain metallic elements and pairs of individual metals (not metal alloys) when produced from mixed precursor solutions in this case.

Polymerization of Methyl Methacrylate with Nickel $\alpha$-Diimine Catalysts: Effect of the Methyl Position in the Ligand

  • Kim, Il;Kim, Jae-Sung;Han, Byeong-Heui;Ha, Chang-Sik
    • Macromolecular Research
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    • v.11 no.6
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    • pp.514-517
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    • 2003
  • In the solution polymerizations of methyl methacrylate with (${\alpha}$-diimine)nickel(II)/methylaluminoxane (MAO), we observed effects of the position of two methyl substituents in the ligand on both the activities of the catalysts and the polymer microstructure. ${\alpha}$-Diimine nickel(II) catalysts gave syndiotactic-rich poly(methyl methacrylate) with high molecular weight and narrow molecular weight distribution.

Effect of B-Cation Doping on Oxygen Vacancy Formation and Migration in LaBO3: A Density Functional Theory Study

  • Kwon, Hyunguk;Park, Jinwoo;Kim, Byung-Kook;Han, Jeong Woo
    • Journal of the Korean Ceramic Society
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    • v.52 no.5
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    • pp.331-337
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    • 2015
  • $LaBO_3$ (B = Cr, Mn, Fe, Co, and Ni) perovskites, the most common perovskite-type mixed ionic-electronic conductors (MIECs), are promising candidates for intermediate-temperature solid oxide fuel cell (IT-SOFC) cathodes. The catalytic activity on MIEC-based cathodes is closely related to the bulk ionic conductivity. Doping B-site cations with other metals may be one way to enhance the ionic conductivity, which would also be sensitively influenced by the chemical composition of the dopants. Here, using density functional theory (DFT) calculations, we quantitatively assess the activation energies of bulk oxide ion diffusion in $LaBO_3$ perovskites with a wide range of combinations of B-site cations by calculating the oxygen vacancy formation and migration energies. Our results show that bulk oxide ion diffusion dominantly depends on oxygen vacancy formation energy rather than on the migration energy. As a result, we suggest that the late transition metal-based perovskites have relatively low oxygen vacancy formation energies, and thereby exhibit low activation energy barriers. Our results will provide useful insight into the design of new cathode materials with better performance.

Synthesis of Methanol and Formaldehyde by Partial Oxidation of Methane over Mixed Oxide Catalysts (복합산화물 촉매 상에서 메탄의 부분산화에 의한 메탄올 및 포름알데히드의 합성)

  • Hahm, Hyun-Sik;Shin, Ki-Seok;Ahn, Sung-Hwan;Kim, Song-Hyoung;Hong, Seok-Young;Park, Hong-Soo
    • Journal of the Korean Applied Science and Technology
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    • v.23 no.3
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    • pp.223-229
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    • 2006
  • Methanol and formaldehyde were produced directly by the partial oxidation of methane over mixed oxide catalysts. The catalysts were composed of Mo and Bi with late-transition metals, such as Mn, Fe, and Co. The reaction was carried out at $450^{\circ}C$, 50 bar in a fixed-bed differential reactor. The prepared catalysts were characterized by $O_2-TPD$ and BET apparatus. Among the catalysts used, the catalyst composed of 1:1:2.5 molar ratio of Mo:Bi:Mn showed the best methane conversion and methanol selectivity. The change in ratio of methane to oxygen affected at the conversion and selectivity, and the most proper ratio was 10:1.5. Methane conversion, methanol and formaldehyde selectivities increased with the surface areas of the catalysts. From the $O_2-TPD$ result, it was found that the oxygen species responsible for this reaction might be the lattice oxygen species desorbed at high temperature around $800^{\circ}C$.

Synthesis of Methanol and Formaldehyde by Partial Oxidation of Methane (메탄의 부분산화에 의한 메탄올 및 포름알데히드의 합성)

  • Hahm, Hyun-Sik;Shin, Ki-Seok;Kim, Song-Hyoung;Ahn, Sung-Hwan;Kim, Myung-Soo;Park, Hong-Soo
    • Journal of the Korean Applied Science and Technology
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    • v.23 no.1
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    • pp.63-69
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    • 2006
  • Methanol and formaldehyde were produced directly by the partial oxidation of methane. The catalysts used were mixed oxides of late-transition metals, such as Mn, Fe, Co, Ni and Cu. The reaction was carried out at $450^{\circ}C$, 50 bar in a fixed-bed differential reactor. The prepared catalysts were characterized by XRD, TPD and BET apparatus. Of the catalysts, A-Mn0.2-6, which contains 0.2 mole of Mn and calcined at $600^{\circ}C$, showed the best catalytic activity: 3.7% methane conversion, and 30 and 28% methanol and formaldehyde selectivities, respectively. The catalytic activity was changed with the content of Mn and the calcination temperature. Catalytic activity increased with the specific surface areas of the catalysts. With XRD, it was found that the structure of the catalysts are changed with calcination temperature. Through $O_2-TPD$ experiment, it was found that the catalysts showing good catalytic activity showed $O_2$ desorption peak around $800^{\circ}C$.

Temporal Variations of Ore Mineralogy and Sulfur Isotope Data from the Boguk Cobalt Mine, Korea: Implication for Genesis and Geochemistry of Co-bearing Hydrothermal System (보국 코발트 광상의 산출 광물종 및 황동위원소 조성의 시간적 변화: 함코발트 열수계의 성인과 지화학적 특성 고찰)

  • Yun, Seong-Taek;Youm, Seung-Jun
    • Economic and Environmental Geology
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    • v.30 no.4
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    • pp.289-301
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    • 1997
  • The Boguk cobalt mine is located within the Cretaceous Gyeongsang Sedimentary Basin. Major ore minerals including cobalt-bearing minerals (loellingite, cobaltite, and glaucodot) and Co-bearing arsenopyrite occur together with base-metal sulfides (pyrrhotite, chalcopyrite, pyrite, sphalerite, etc.) and minor amounts of oxides (magnetite and hematite) within fracture-filling $quartz{\pm}actinolite{\pm}carbonate$ veins. These veins are developed within an epicrustal micrographic granite stock which intrudes the Konchonri Formation (mainly of shale). Radiometric date of the granite (85.98 Ma) indicates a Late Cretaceous age for granite emplacement and associated cobalt mineralization. The vein mineralogy is relatively complex and changes with time: cobalt-bearing minerals with actinolite, carbonates, and quartz gangues (stages I and II) ${\rightarrow}$ base-metal sulfides, gold, and Fe oxides with quartz gangues (stage III) ${\rightarrow}$ barren carbonates (stages IV and V). The common occurrence of high-temperature minerals (cobalt-bearing minerals, molybdenite and actinolite) with low-temperature minerals (base-metal sulfides, gold and carbonates) in veins indicates a xenothermal condition of the hydrothermal mineralization. High enrichment of Co in the granite (avg. 50.90 ppm) indicates the magmatic hydrothermal derivation of cobalt from this cooling granite stock, whereas higher amounts of Cu and Zn in the Konchonri Formation shale suggest their derivations largely from shale. The decrease in temperature of hydrothermal fluids with a concomitant increase in fugacity of oxygen with time (for cobalt deposition in stages I and II, $T=560^{\circ}C-390^{\circ}C$ and log $fO_2=$ >-32.7 to -30.7 atm at $350^{\circ}C$; for base-metal sulfide deposition in stage III, $T=380^{\circ}-345^{\circ}C$ and log $fO_2={\geq}-30.7$ atm at $350^{\circ}C$) indicates a transition of the hydrothermal system from a magmatic-water domination toward a less-evolved meteoric-water domination. Sulfur isotope data of stage II sulfide minerals evidence that early, Co-bearing hydrothermal fluids derived originally from an igneous source with a ${\delta}^{34}S_{{\Sigma}S}$ value near 3 to 5‰. The remarkable increase in ${\delta}^{34}S_{H2S}$ values of hydrothermal fluids with time from cobalt deposition in stage II (3-5‰) to base-metal sulfide deposition in stage III (up to about 20‰) also indicates the change of the hydrothermal system toward the meteoric water domination, which resulted in the leaching-out and concentration of isotopically heavier sulfur (sedimentary sulfates), base metals (Cu, Zn, etc.) and gold from surrounding sedimentary rocks during the huge, meteoric water circulation. We suggest that without the formation of the later, meteoric water circulation extensively through surrounding sedimentary rocks the Boguk cobalt deposits would be simple veins only with actinolite + quartz + cobalt-bearing minerals. Furthermore, the formation of the meteoric water circulation after the culmination of a magmatic hydrothermal system resulted in the common occurrence of high-temperature minerals with later, lower-temperature minerals, resulting in a xenothermal feature of the mineralization.

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