• Title/Summary/Keyword: $Ru_2CO_3$

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Synthesis of Novel Electrochemiluminescent Polyamine Dendrimers Functionalized with Polypyridyl Ru(II) Complexes and Their Electrochemical Properties

  • Lee, Do-Nam;Park, Hee-Sang;Kim, Eun-Hwa;Jun, Young-Moo;Lee, Ja-Young;Lee, Won-Yong;Kim, Byeong-Hyo
    • Bulletin of the Korean Chemical Society
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    • v.27 no.1
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    • pp.99-105
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    • 2006
  • Polyamine dendrimers functionalized with electrochemiluminescent (ECL) polypyridyl Ru(II) complexes, dend-$[CO-(CH_2)_3-mbpy{\cdot}Ru(L)_2]_3(PF_6)_6$ (dend: N$(CH_2CH_2NH)_3$-, L: bpy, o-phen, phen-Cl, DTDP), were synthesized through the complexation of dendritic polypyridyl ligands to Ru(II) complexes. Their electrochemical redox potentials, photoluminescence (PL), and relative ECL intensities were studied. The ECL emissions produced by the reaction between the electro-oxidized $Ru^{3+}$ species of polyamine dendrimers and tripropylamine as a coreactant were measured in a static system with potential cycles between 0.8 and 1.3 V or through flow injection analysis with a potential of +1.3 V, and were compared to that of $[Ru(o-phen)_3](PF_6)_2{\cdot}Dend-[CO-(CH_2)_3-mbpy{\cdot}Ru(bpy)_2]_3(PF_6)_6$ showed an ECL intensity that was two-fold greater than that of the reference complex $[Ru(o-phen)_3](PF_6)_2$.

Development of Monolithic Catalyst System with Co-Ru-Zr for CO2 (dry) Reforming of Methane : Enhanced Coke Tolerance

  • Kim, Hyojin;You, Young-Woo;Heo, Iljeong;Chang, Tae-Sun;Hong, Ji Sook;Lee, Ki Bong;Suh, Jeong Kwon
    • Clean Technology
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    • v.23 no.3
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    • pp.314-324
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    • 2017
  • To verify the viability of Co, Ru and Zr-based catalyst for $CO_2$ (dry) reforming reaction, catalysts were fabricated using cordierite, silicon carbide and rota monolithic substrates, and they were compared with the conventional $Co-Ru-Zr/SiO_2$ catalyst in terms of performance and durability. Cordierite monolith was showed high activity with the least amount of active component. In addition, when Cordierite monolith was coated with Co-Ru-Zr in various ways, most excellent performance was showed at a precursor solution coating method. In particular, when 0.9 wt% Co-Ru-Zr/Cordierite was used for reaction, it was observed that 95% $CO_2$ conversion was maintained for 300 h at $900^{\circ}C$.

A Density Functional Theory Investigation on Intramolecular Hydrogen Transfer of the [Os3(CO)11P(OMe)3(Ru(η5-C5H5))2] Cluster

  • Buntem, Radchada;Punyain, Kraiwan;Tantirungrotechai, Yuthana;Raithby, Paul R.;Lewis, Jack
    • Bulletin of the Korean Chemical Society
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    • v.31 no.4
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    • pp.934-940
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    • 2010
  • The reduction of [$Os_3(CO)_{11}P(OMe)_3$] and subsequent ionic coupling of the reduced species with $[Ru({\eta}^5-C_5H_5)(CH_3CN)_3]^+$ resulted in the formation of [$Os_3(CO)_{11}P(OMe)_3(Ru({\eta}^5-C_5H_5))_2$] which can be converted to spiked tetrahedral cluster, [$HOs_3(CO)_{11}P(OMe)_3Ru_2({\eta}^5-C_5H_5)(C_5H_4)$] via the intramolecular hydrogen transfer. Due to the unavailability of a suitable single crystal, the PW91/SDD and LDA/SDD density functional methods were used to predict possible structures and the available spectroscopic information (IR, NMR) of [$Os_3(CO)_{11}P(OMe)_3(Ru({\eta}^5-C_5H_5))_2$]. The most probable geometry found by constrained search is the isomer (a2) in which the phosphite, $P(OMe)_3$, occupies an axial position on one of the two osmium atoms that is edge bridged by the $Ru(CO)_2({\eta}^5-C_5H_5)$ unit. By using the most probably geometry, the predicted infrared frequencies and $^1H$, $^{13}C$ and $^{31}P$ NMR chemical shifts of the compound are in the same range as the experimental values. For this type of complex, the LDA/SDD method is appropriate for IR predictions whereas the OPBE/IGLO-II method is appropriate for NMR predictions. The activation energy and reaction energy of the intramolecular hydrogen transfer coupled with the structural change of the transition metal framework were estimated at the PW91/SDD level to be 110.32 and -0.14 kcal/mol respectively.

Synthesis and Reactions of Organoruthenium(Ⅲ) Complexes (새로운 3가 유기루테늄 착물의 합성과 반응)

  • Lee Dong-Hwan;Kim Hag-Gu;Seo Dae-Ryong;Kim Byung-Soon
    • Journal of the Korean Chemical Society
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    • v.37 no.1
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    • pp.98-104
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    • 1993
  • The paramagnetic organoruthenium(III) complexes $({\eta}^5-C_5Me_5)RuCl_2(PR_3) (PR_3 = PMe_3,\;PEt_3,\;PiPr_3,\;PCy_3,\;PMe_2Ph,\;PMePh_2,\;PPh_3,\;P(p-C_6H_4CH_3)_3$, DPPE, DPPB, Py) (2a∼2k) were synthesized by the reaction of $[({\eta}^5-C_5Me_5)RuCl_2]_2$ (1) with 1 equivalent of the corresponding phosphines $(PR_3)$. The effective magnetic moment ((${\mu}_{eff} = 1.65∼2.07 B.M.$)) derived from the magnetic susceptibility measurements of the complexes (2a∼2k) were consistent with the presence of a "single" unpaired electron in the molecule. Treatment of dichlororuthenium (III) complex ({\eta}^5-C_5Me_5)RuCl_2(PR_3)$ (2) (i) with KBr in acetone afforded the dibromoruthenium (III) complex $({\eta}^5-C_5Me_5)RuBr_2(PR_3) (PR_3 = PPh_3)$, (ii) with sodium amalgam in diethylether led to the bis(phosphine) derivatives $({eta}^5-C_5Me_5)RuCl(PR_3)_2 (PR_3 = PMe_3,\;PMePh_2)$, and (iii) with carbonmonoxide gave to the carbonyl derivatives $({\eta}^5-C_5Me_5)RuCl(PR_3)(CO) (PR_3 = PMe_3,\;PPh_3)$.

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Ruthenium Complex-catalyzed Highly Selective Co-oligomerization of Alkenes

  • Ura, Yasuyuki;Tsujita, Hiroshi;Mitsudo, Take-Aki;Kondo, Teruyuki
    • Bulletin of the Korean Chemical Society
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    • v.28 no.12
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    • pp.2139-2152
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    • 2007
  • Ruthenium complex-catalyzed reactions often require highly qualified tuning of reaction conditions with substrates to attain high yield and selectivity of the products. In this review, our strategies for achieving characteristic ruthenium complex-catalyzed co-oligomerization of different alkenes are disclosed: 1) The codimerization of 2-norbornenes with acrylic compounds by new ruthenium catalyst systems of RuCl3(tpy)/Zn [tpy = 2,2':6',2''-terpyridine] or [RuCl2(η6-C6H6)]2/Zn in alcohols, 2) A novel synthesis of 2-alkylidenetetrahydrofurans from dihydrofurans and acrylates by zerovalent ruthenium catalysts, such as Ru(η4-cod)(η6-cot) [cod = 1,5-cyclooctadiene, cot = 1,3,5-cyclooctatriene] and Ru(η6-cot)(η2-dmfm)2 [dmfm = dimethyl fumarate], 3) Regio- and stereoselective synthesis of enamides by Ru(η6-cot)(η2-dmfm)2-catalyzed codimerization of N-vinylamides with alkenes, and 4) Unusual head-to-head dimerization of styrenes and linear codimerization of styrenes with ethylene by Ru(η6-cot)(η2-dmfm)2 catalyst in the presence of primary alcohols.

Effect of Tungsten on PtRuW/C Catalysts for Promoting Methanol Electro-oxidation (메탄올 전기산화반응 증진을 위한 PtRuW/C 촉매에서 텅스텐의 효과에 관한 연구)

  • Noh, Chang Soo;Sohn, Jung Min;Park, Young-Kwon
    • Applied Chemistry for Engineering
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    • v.23 no.6
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    • pp.561-566
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    • 2012
  • PtRuW/C catalysts were prepared with the different molar ratios of Pt : Ru : W and their compositions were analyzed by energy dispersive X-ray (EDX). The uniform distribution of particles was observed using transmission electron microscopy (TEM). An average crystalline size of 3.5~5.5 nm was calculated based on x-ray diffraction (XRD) data. The electrochemical properties such as electrochemically active surface areas, current densities, specific activities and poisoning rates, were analyzed via CO stripping, linear sweep voltammetry and chronoamperometry. From the analysis, we observed that ternary alloy catalysts, except $PtRu_2W_2/C$, have higher current densities, specific activities and stabilities than those of commercial binary catalysts. Among all in-house catalysts, Pt5Ru4W/C showed the highest specific activity of $121.05mA{\cdot}m^{-2}$ and the lowest poisoning rate of $0.01%{\cdot}s^{-1}$.

Silicide Formation of Atomic Layer Deposition Co Using Ti and Ru Capping Layer

  • Yoon, Jae-Hong;Lee, Han-Bo-Ram;Gu, Gil-Ho;Park, Chan-Gyung;Kim, Hyung-Jun
    • Korean Journal of Materials Research
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    • v.22 no.4
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    • pp.202-206
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    • 2012
  • $CoSi_2$ was formed through annealing of atomic layer deposition Co thin films. Co ALD was carried out using bis(N,N'-diisopropylacetamidinato) cobalt ($Co(iPr-AMD)_2$) as a precursor and $NH_3$ as a reactant; this reaction produced a highly conformal Co film with low resistivity ($50\;{\mu}{\Omega}cm$). To prevent oxygen contamination, $ex-situ$ sputtered Ti and $in-situ$ ALD Ru were used as capping layers, and the silicide formation prepared by rapid thermal annealing (RTA) was used for comparison. Ru ALD was carried out with (Dimethylcyclopendienyl)(Ethylcyclopentadienyl) Ruthenium ((DMPD)(EtCp)Ru) and $O_2$ as a precursor and reactant, respectively; the resulting material has good conformality of as much as 90% in structure of high aspect ratio. X-ray diffraction showed that $CoSi_2$ was in a poly-crystalline state and formed at over $800^{\circ}C$ of annealing temperature for both cases. To investigate the as-deposited and annealed sample with each capping layer, high resolution scanning transmission electron microscopy (STEM) was employed with electron energy loss spectroscopy (EELS). After annealing, in the case of the Ti capping layer, $CoSi_2$ about 40 nm thick was formed while the $SiO_x$ interlayer, which is the native oxide, became thinner due to oxygen scavenging property of Ti. Although Si diffusion toward the outside occurred in the Ru capping layer case, and the Ru layer was not as good as the sputtered Ti layer, in terms of the lack of scavenging oxygen, the Ru layer prepared by the ALD process, with high conformality, acted as a capping layer, resulting in the prevention of oxidation and the formation of $CoSi_2$.

A Novel Method for Preparing of Oxoruthenates Complexes: trans-[RuO3(OH)2]2-, [RuO4]-, (n-Pr4N)+[RuO4]- and [RuO4 and Their Use as Catalytic Oxidants

  • Shoair, Abdel-Ghany F.
    • Bulletin of the Korean Chemical Society
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    • v.26 no.10
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    • pp.1525-1528
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    • 2005
  • The synthesis and characterization of ${K_3[Ru(C_2O_4)3]{\cdot}4H_2O\;(C_2O_4}^{2-}$ = oxalato anoin) complex are described, and its redox properties (in buffer solution of pH = 12) have been investigated. This complex is used for in situ generation of oxoruthenates complexes which have been characterized by electronic spectroscopy. Reaction of ${K_3[Ru(C_2O_4)3]{\cdot}4H_2O$ with excess ${S_2O_8}^{2-}$ in molar KOH generates trans-${[RuO_3(OH)_2]^{2-}/S_2O_8}^{2-}$ reagent while with excess ${BrO_3}^-$ in molar $Na_2CO_3$ generates ${[RuO_4]^-/BrO_3}^-$ reagent. Avoiding the direct use of [$RuO_4$] the organic-soluble $(n-Pr_4N)^+[RuO_4]^-$, (TPAP) has been isolated by reaction of $K_3[Ru(C_2O_4)3]{\cdot}4H_2O$ with excess ${BrO_3}^-$ in molar carbonate and n-$Pr_4$NOH. In a mixture of $H_2O/CCl_4$ ruthenium tetraoxide can be generated by reaction of $K_3[Ru(C_2O_4)3]{\cdot}4H_2O$ with excess ${IO_4}^-$. The catalytic activities of oxoruthenates that have been made from $K_3[Ru(C_2O_4)3]{\cdot}4H_2O$ towards the oxidation of benzyl alcohol, piperonyl alcohol, benzaldehyde and benzyl amine at room temperature have been studied.

Electrocatalytic Performances of La0.6Ca0.4CoO3 and Pb2Ru2O6 prepared by Amorphous Citrate Precursor Method (Amorphous Citrate Precursor 법으로 제조한 La0.6Ca0.4CoO3와 Pb2Ru2O6의 전기화학적 촉매능)

  • Lee, Churl Kyoung;Sohn, Hun-Joon
    • Applied Chemistry for Engineering
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    • v.10 no.3
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    • pp.331-335
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    • 1999
  • The transition metal oxides have been of interest as bifunctional electrocatalysts for bifunctional air electrodes. The amorphous citrate precursor (ACP) process has been optimized to prepare perovskite (La0.6Ca0.4CoO3) and pyrochlore (Pb2Ru2O6) powders with high surface area, and consequent improvement of The electrocatalytic performance in an air electrode with thermal treatment. PTFE -bonded gas diffusion electrodes loaded with perovskitc and pyrochlore catalysts showed good bifunctional performances. The electrodes were fairly stable up to 100 hour in the galvanostatic mode at ${\pm}25mA/cm^2$, from which these electrodes offer promise as practical bifunctional air electrodes.

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Switching Characteristics of Magnetic Tunnel Junction with Amorphous CoFeSiB Free Layer (비정질 CoFeSiB 자유층을 갖는 자기터널접합의 스위칭 특성)

  • Hwang, J.Y.;Rhee, J.R.
    • Journal of the Korean Magnetics Society
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    • v.16 no.6
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    • pp.276-278
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    • 2006
  • The switching characteristics of magnetic tunnel junctions (MTJs) comprising amorphous ferromagnetic CoFeSiB free layer have been investigated. CoFeSiB was used for the free layer to enhance the switching characteristics. The typical junction structure was $Si/SiO_{2}/Ta$ 45/Ru 9.5/IrMn 10/CoFe $7/AlO_{x}/CoFeSiB\;(t)/Ru\;60\;(in\;nm)$. CoFeSiB has low saturation magnetization ($M_{s}$) of $560\;emu/cm^{3}$ and high anisotropy constant ($K_{u}$) of $2800\;erg/cm^{3}$. These properties caused low coercivity ($H_{c}$) and high sensitivity in MTJs, and it also confirmed in submicrometer-sized elements by micromagnetic simulation based on the Landau-Lisfschitz-Gilbert equation. By increasing CoFeSiB free layer thickness, the switching characteristics became worse due to increase of the demagnetization field.