• Title/Summary/Keyword: Palladium catalysts

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Electrocatalytic Activity of Platinum-palladium Catalysts Prepared by Sequential Reduction Methods (순차적 환원 방법으로 제조된 백금-팔라듐 촉매의 전기 활성)

  • Park, Jae Young;Park, Soo-Jin;Jung, Yongju;Kim, Seok
    • Applied Chemistry for Engineering
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    • v.23 no.2
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    • pp.153-156
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    • 2012
  • In this study, two different methods were studied to prepare Pt-Pd catalysts for direct methanol fuel cells in order to enhance the electrochemical efficiency. The catalysts were compared with simultaneously deposited Pt-Pd and sequentially deposited Pt-Pd. The electrocatalysts contained 20 wt% of metal loading on carbon black and 1 : 2 of Pt : Pd atomic ratio. Electrochemical properties of the catalysts were compared by measuring cyclic voltammetries and average sizes and lattice parameters were measured by transmission electron microscopy images and x-ray diffraction. As a result, sequentially deposited Pt-Pd/C catalysts showed better electrochemical properties than those of simultaneously deposited Pt-Pd/C catalysts.

Palladium-Catalyzed Carbonylative Homocoupling Reaction of Vinylmercuric Chlorides with Carbon Monoxide (팔라듐 촉매를 이용한 Vinylmercuric-chlorides 의 CO 첨가 호모커플링반응)

  • KimJin-Il 김진일;Kwang-Hyek Lee
    • Journal of the Korean Chemical Society
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    • v.33 no.6
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    • pp.657-661
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    • 1989
  • Symmetrical divinyl ketone or divinyl ${\alpha}$-diketone was synthesized in moderately good yields through palladium catalyzed carbonylative homocoupling reaction of vinylmercuric chlorides with carbon monoxide. In order to find out optimum synthetic reaction conditions, we examined the effect of catalysts, bases, solvents and reaction temperature when (E)-styrylmercuric chloride was used as a typical starting material. The best yield of divinyl ${\alpha}$-diketone was obtained in the reaction using 10 mol% of dichlorobis(triphenyl phosphine)palladium (II) as a catalyst, an equivalent of pyridine as a base, 10 mol% of iodine and acetonitrile at 50${\circ}$C under 10 atmospheric pressure of carbon monoxide. The yield of divinyl ${\alpha}$-diketone was decreased under atmospheric pressure of carbon monoxide.

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Ligand Effect in Recycled CNT-Pd Heterogeneous Catalyst for Decarboxylative Coupling Reactions

  • Kim, Ji Dang;Pyo, Ayoung;Park, Kyungho;Kim, Gwui Cheol;Lee, Sunwoo;Choi, Hyun Chul
    • Bulletin of the Korean Chemical Society
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    • v.34 no.7
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    • pp.2099-2104
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    • 2013
  • We present here an efficient and simple method for preparation of highly active Pd heterogeneous catalyst (CNT-Pd), specifically by reaction of dichlorobis(triphenylphosphine)palladium ($Pd(PPh_3)_2Cl_2$) with thiolated carbon nanotubes (CNTs). The as-prepared CNT-Pd catalysts demonstrated an excellent catalytic activity for the carbon-carbon (C-C) cross-coupling reactions (i.e. Suzuki, Stille, and decarboxylative coupling reactions) under mild conditions. The CNT-Pd catalyst could easily be removed from the reaction mixture; additionally, in the decarboxylative coupling of iodobenzene and phenylpropiolic acid, it showed a six-times recyclability, with no loss of activity. Moreover, once its activity had decreased by repeated recycling, it could easily be reactivated by the addition of phosphine ligands. The remarkable recyclability of the decarboxylative coupling reaction is attributable to the high degree of dispersion of Pd catalysts in CNTs. Aggregation of the Pd catalysts is inhibited by their strong adhesion to the thiolated CNTs during the chemical reactions, thereby permitting their recycling.

Dynamic Kinetic Resolutions and Asymmetric Transformations by Enzyme-Metal Combo Catalysis

  • Kim, Mahn-Joo;Ahn, Yang-Soo;Park, Jai-Wook
    • Bulletin of the Korean Chemical Society
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    • v.26 no.4
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    • pp.515-522
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    • 2005
  • Enzyme-metal combo catalysis is described as a useful methodology for the synthesis of optically active compounds. The key point of the method is the use of enzyme and metal in combination as the catalysts for the complete transformation of racemic substrates to single enantiomeric products through dynamic kinetic resolution (DKR). In this approach, enzyme acts as an enantioselective resolving catalyst and metal does as a racemizing catalyst for the efficient DKR. Three kinds of enzyme-metal combinations - lipase-ruthenium, subtilisin-ruthenium, and lipase-palladium –have been developed as the catalysts for the DKRs of racemic alcohols, esters, and amines. The scope of the combination catalysts can be extended to the asymmetric transformations of ketones, enol acetates, and ketoximes via the DKRs. In most cases studied, enzyme-metal combo catalysis provided enantiomerically-enriched products in high yields.

Chiral [Iminophosphoranyl]ferrocenes: Synthesis, Coordination Chemistry, and Catalytic Application

  • Co, Thanh Thien;Shim, Sang-Chul;Cho, Chan-Sik;Kim, Dong-Uk;Kim, Tae-Jeong
    • Bulletin of the Korean Chemical Society
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    • v.26 no.9
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    • pp.1359-1365
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    • 2005
  • A series of new chiral [iminophosphoranyl]ferrocenes, {${\eta}^5-C_5H_4-(PPh_2=N-2,6-R_2-C_6H_3)$}Fe{${\eta}^5-C_5H_3-1-PPh^2-2-CH(Me)NMe_2$} (1: R = Me, $^iPr$), {${\eta}^5{-C_5H_4-(PPh_2=N-2,6-R_2}^1-C_6H_3)$}Fe{${\eta}^5-C_5H_3-1-(PPh_2=N-2,6-R_2-C_6H_3)-2-CH(Me)R_2$} (2: $R^1\;=\;Me,\;^iPr;\;R^2\;=\;NMe_2$, OMe), and $({\eta}^5-C_5H_5)Fe${${\eta}^5-C_5H_4-1-PR_2-2-CH(Me)N=PPh_3$} (3:R = Ph, $C_6H_{11}$) have been prepared from the reaction of [1,1'-diphenylphosphino-2-(N,N-dimethylamino) ethyl]ferrocene with arylazides (1 & 2) and the reaction of phosphine dichlorides ($R_3PCl_{2}$) with [1,1'-diphenylphosphino-2-aminoethyl]ferrocene (3), respectively. They form palladium complexes of the type $[Pd(C_3H_5)(L)]BF_4$ (4-6: L = 1-3), where the ligand (L) adopts an ${\eta}^2-N,N\;(2)\;or\;{\eta}^2$-P,N (3) as expected. In the case of 1, a potential terdentate, an ${\eta}^2$-P,N mode is realized with the exclusion of the –=NAr group from the coordination sphere. Complexes 4-6 were employed as catalysts for allylic alkylation of 1,3-diphenylallyl acetate leading to an almost stoichiometric product yield with modest enantiomeric excess (up to 74% ee). Rh(I)-complexes incorporating 1-3 were also prepared in situ for allylic alkylation of cinnamyl acetate as a probe for both regio- and enantioselectivities of the reaction. The reaction exhibited high regiocontrol in favor of a linear achiral isomer regardless of the ligand employed.

Catalytic Oxidation of Toluene over Pd-Activated Alumina Catalysts at Low Temperature (활성알루미나에 담지한 팔라듐 촉매상에서 톨루엔의 저온 연소반응)

  • Lee, Ju-Yeol;Song, Hyung-Jin;Lee, Sang-Bong;Kim, Mi-Hyung;Jo, Young-Min
    • Journal of the Korean Applied Science and Technology
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    • v.29 no.2
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    • pp.339-347
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    • 2012
  • This study focuses on developing catalysts for the removal of toluene produced from paint booth. Toluene is one of the major VOC in painting, coating process. Pd catalysts have been used in hydrogenation oxidation and low temperature combustion reaction for toluene removal. Pd catalysts, even though it is very precious and expensive. Therefore, the prepared catalysts from minimizing the amount of Pd ratio (0.1~1.0wt%) were measured. As a result, 1.0wt% Pd(R) catalyst under all conditions showed the highest activity. These results may suggest that the catalytic activity is related to Pd dispersion according sintering atmosphere and Pd ratio in the manufacturing process through the analysis of SEM, XRD.

The Study of Toluene Combustion over Palladium-copper/USY Zeolite Catalyst (Pd-Cu/USY 제올라이트상에서 톨루엔 연소반응 연구)

  • Lee, Hye Young;Jin, Taihuan;Hwang, Young Kyu;Chang, Jong-San;Hwang, Jin-Soo;Lee, Chang-Gook;Baek, Shin;Ra, Do-Young
    • Korean Chemical Engineering Research
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    • v.44 no.4
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    • pp.404-409
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    • 2006
  • The catalytic combustion of toluene over Pd-Cu/USY zeolite has been examined by using FT-IR spectroscopy in a closed system under dry and humid conditions. The catalytic combustion of toluene (700 ppmv) in the temperature range of $80-220^{\circ}C$ has been investigated by using a fixed bed reactor. The Pd-Cu/USY catalyst showed the highest catalytic performance with respects to the PdO-CuO/USY and Pd/USY. Comparing to $PdO/Al_2O_3$ catalysts, the slight improvement in conversion was observed over PdO/USY catalysts under humid condition since USY zeolite is hydrophobic substrate and water give an additional oxygen source to zeolite surface like oxygen. The reduced catalysts showed more enhanced catalytic activity due to the reduced activation energy of combustion of toluene than oxidized catalysts such as PdO/USY and PdO-CuO/USY.

Synthesis and Characterization of Graphene and Graphene Oxide Based Palladium Nanocomposites and Their Catalytic Applications in Carbon-Carbon Cross-Coupling Reactions

  • Lee, Minjae;Kim, Bo-Hyun;Lee, Yuna;Kim, Beom-Tae;Park, Joon B.
    • Bulletin of the Korean Chemical Society
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    • v.35 no.7
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    • pp.1979-1984
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    • 2014
  • We have developed an efficient method to generate highly active Pd and PdO nanoparticles (NPs) dispersed on graphene and graphene oxide (GO) by an impregnation method combined with thermal treatments in $H_2$ and $O_2$ gas flows, respectively. The Pd NPs supported on graphene (Pd/G) and the PdO NPs supported on GO (PdO/GO) demonstrated excellent carbon-carbon cross-coupling reactions under a solvent-free, environmentally-friendly condition. The morphological and chemical structures of PdO/GO and Pd/G were fully characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). We found that the remarkable reactivity of the Pd/G and PdO/GO catalysts toward the cross-coupling reaction is attributed to the high degree of dispersion of the Pd and PdO NPs while the oxidative states of Pd and the oxygen functionalities of graphene oxide are not critical for their catalytic performance.

Preparation of Graphene Based PdOx and CuOx/MnOx Nanocomposites and Their Catalytic Applications in C-C Coupling and CH3SH Decomposition Reactions

  • Lee, Gyeong-Hun;Park, Jun-Beom
    • Proceedings of the Korean Vacuum Society Conference
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    • 2014.02a
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    • pp.175.2-175.2
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    • 2014
  • Graphene (G) has been modified with palladium, copper, and manganese oxide nanoparticles (NPs), and their catalytic applications have been studied in C-C coupling reactions and methylmercaptan (CH3SH) decomposition reactions. In this research, graphite oxide (GO) sheets were exfoliated and oxidized from graphite powder and impregnated with metal precursors including Pd2+, Cu2+, and Mn2+. The thermal treatments of the metal impregnated GO in preferred gas environments produced Pd NPs on graphene (Pd/G), PdO NPs on GO (PdO/GO), and CuOx and MnOx NPs on graphene (CuOx/MnOx/G). In case of Pd/G and PdO/GO, the TEM images show that, although the mean size of the Pd NPs changed significantly before and after the C-C coupling reaction, that of the PdO NPs didn't, implying that the PdO/GO was superior to Pd/G in terms of the recyclability. Also, we demonstrate that the CuOx/MnOx/G exerts the excellent catalytic efficiency in CH3SH decomposition reaction comparing with conventional catalysts. The chemical and electronic structural changes were investigated using XRD and XPS.

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