• Title/Summary/Keyword: Palladium

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Palladium Catalyzed New Synthesis of Divinyl Ketones and Divinyl ${\alpha}$-Diketones (팔라듐 촉매를 이용한 디비닐케톤과 디비닐 ${\alpha}$-디케톤의 새로운 합성)

  • Jin Il Kim;Kwang Hyek Lee;Seung Jae Im
    • Journal of the Korean Chemical Society
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    • v.33 no.5
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    • pp.522-529
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    • 1989
  • Symmetrical divinyl ketones and divinyl ${\alpha}$-diketones were synthesized in moderately good yields through palladium catalyzed carbonylative homocoupling reaction of vinylic halides. Divinyl ${\alpha}$-diketones were obtained in the highest yield in the presence of 10 atm of carbon monoxide, using 2 mol% ligand added to palladium(II) acetate as catalyst and three equivalents of tributylamine as base in polar solvent at $100^{\circ}C$. Divinyl ketones were synthesized mainly under atmospheric pressure of carbon monoxide. The reaction was also proceeded to several other vinylic halides under the above reaction condition. Thus, divinyl ketones and divinyl ${\alpha}$-diketones were synthesized selectively as expected.

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A Study on the Degradation Properties of Aqueous Trinitrotoluene by Palladium Catalyst and Formic Acid (Palladium 촉매와 포름산을 활용한 액상 trinitrotoluene 분해 특성 연구)

  • Jeong, Sangjo;Choi, Hyungjin;Park, Sangjin;Lee, Juneil
    • Journal of Korean Society on Water Environment
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    • v.31 no.5
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    • pp.468-475
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    • 2015
  • Various methods to degrade explosives efficiently in natural soil and water that include trinitrotoluene (TNT) have been studied. In this study, TNT in water was degraded by reduction with palladium (Pd) catalyst impregnated onto alumina (henceforth Pd-Al catalyst) and formic acid. The degradation of TNT was faster when the temperature of water was high, and the initial TNT concentration, pH, and ion concentration in water were low. The amounts of Pd-Al catalyst and formic acid were also important for TNT degradation in water. According to the experimental results, the degradation constant of TNT with unit mass of Pd-Al catalyst was $8.37min^{-1}g^{-1}$. The degradation constant of TNT was higher than the results of previous studies which used zero valent iron. 2,6-diamino-4-nitrotoluene and 2-amino-4,6-dinitrotoluene were detected as by-products of TNT degradation showing that TNT was reduced. The by-products of TNT were also completely degraded after reaction when both Pd-Al catalyst and formic acid existed. Even though there are several challenges of Pd-Al catalyst (e.g., deactivation, poisoning, leaching, etc.), the results of this study show that TNT degradation by Pd-Al catalyst and formic acid is a promising technique to remediate explosive contaminated water and soil.

Carbonylative Cyclization of Unsaturated Carboxylic Acids by Palladium Complexes with Phosphines(I) Synthesis and Structure of Palladium(O, II) Complexes with Unsaturated Carboxylic Acids (포스핀류가 배위된 팔라듐 착물에 의한 불포화카르복실산의 카르보닐화고리 반응 (제 1 보). 불포화카르복실산이 배위된 팔라듐(0, Ⅱ) 착물의 합성과 구조)

  • Myung-Ki Doh;Maeng-Jun Jung;Dong-Jin Lee;Kohtaro Osakada;Akio Yamamoto
    • Journal of the Korean Chemical Society
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    • v.37 no.4
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    • pp.423-430
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    • 1993
  • New Palladium(0)-olefin complexes, $(PMe_3)_2Pd{CH_2=C(CH_3)COOH} \;and\;(PMe_3)_2Pd{(CH_3)CH=CHCOOH}$ have been prepared by treating $Pd(PMe_3)_2$(styrene) with methacrylic acid and trans-crotonic acid, respectively. These complexes were characterized by elemental analysis, IR and $^1H-,\;^{13}C-,\;and\;^{31}P$-NMR spectroscopy. The carboxylic acid entity was found non-bonded with palladium while ${\pi}$-bond is formed between the olefin double bond and Pd(0). The results are compared with the metallacycle formation the reaction of Pd(PMe3)2(styrene) with 3-butenoic acid.

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The Crystal Structure of Bis(ethylenediamine)palladium(II)-Bis(oxalato)palladate(II) (Bis(ethylenediamine)palladium(II)-Bis(oxalato)palladate(II)의 결정구조)

  • Go, Gi-Yeong;Nam, Gung-Hae;Han, Sang-Gon
    • Korean Journal of Crystallography
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    • v.9 no.1
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    • pp.71-76
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    • 1998
  • Crystal structure of Bis(ethylenediamine)palladium(II)-Bis(oxalato)palladate(II0 has been determined by X-ray crystallography. Crystal data : (Pd(C2H8N2)2.Pd(C2O4)2), Fw=509.04, Monocline, Space Group P21/c (no=14), a=6.959(2), b=13.506(2), c=15.339(2) Å, β=99.94(3), Z=4, V=1420 Å3, Dc=2.380 gcm-3, μ=25.46cm-1, F(000)=992. The intensity data were collected with Mo-Kα radiation (λ=0.7107 Å) on an automatic four-circle diffractometer with a graphite monochromater. The structure was solved by Patterson method and refined by full matrix least-square methods using unit weights. The final R and S values were R=0.021, Rw=0.030, Rall=0.032 abd S=2.1 for 1472 observed reflections. The essentially planar complex anions form diade of interplanar distances of 3.41 Å and their diads are stacked along aaxis with interplanar separation of 3.44 Å.

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Electrochemical Corrosion Characteristics of Dental Prostheses High-Palladium Alloys (치과용 고-Pd계 합금의 부식특성)

  • 김기주;이진형
    • Journal of Biomedical Engineering Research
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    • v.22 no.6
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    • pp.511-518
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    • 2001
  • In vitro corrosion resistance of the commercially used 76.5wt.%Pd-17.6%Cu-7.2%Ga and 77.3%Pd-6.0%Ga dental Prostheses high-Palladium system alloys in cast, degassing and porcelain-firing heat treatment conditions were evaluated by the potentiodynamic polarization technique in the de-aerated 0.9%NaCl and a modified Fusayama electrolyte. From the corrosion rate experimental results, we found that there is a small difference in the corrosion resistance depending on the microstructure. However. it was so small that there is no significant problem as a dental material. The 77.3%Pd-6.0%Ga showed better corrosion resistance than the 76.5%Pd-11.6%Cu-7.2%Ga dental Prostheses high-palladium system alloys. These experimental observations in 76.5%Pd-11.6%Cu-7.2%Ga alleys are mainly due to a rapid quenching and Cu in the alloy which accelerate the eutectic reaction with a segregation and Precipitates in the microstructure. On the ocher hand, 77.3%Pd-6.0%Ga alloys, which are solid-solution matrix, show much better col·lesion resistance compared with that of 76.5%Pd-11.6%Cu-7.2%Ga alloys.

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A STUDY ON THE GALVANIC CORROSION OF TITANIUM USING THE IMMERSION AND ELECTROCHEMICAL METHOD (침적법과 전기화학법을 이용한 티타늄의 갈바닉 부식에 관한 연구)

  • Kay, Kee-Sung;Chung, Chae-Heon;Kang, Dong-Wan;Kim, Byeong-Ok;Hwang, Ho-Gil;Ko, Yeong-Mu
    • The Journal of Korean Academy of Prosthodontics
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    • v.33 no.3
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    • pp.584-609
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    • 1995
  • The purpose of this study was to evaluate the difference of the galvanic corrosion behaviour of the titanium in contact with gold alloy, silva-palladium alloy, and nickel-chromium alloy using the immersion and electrochemical method. And the effects of galvallit couples between titanium and the dental alloys were assessed for their usefulness as materials for superstructure. The immersion method was performed by measuring the amount of metal elementsreleased by Inductivey coupled plasma emission spectroscopy(ICPES) The specimen of fifteen titanium plates, the five gold alloy, five silver-palladium, five nickel-chromium plates, and twenty acrylic resin plates ware fabricated, and also the specimen of sixty titanium plugs, the thirty gold alloy, thirty silver-palladium, and nickelc-hromium plugs were made. Thereafter, each plug of gold alloy, silver-palladium, and nickel-chromium inserted into the the titanium and acrylic resin plate, and also titanium plug inserted into the acrylic resin plate. The combination specimens uf galvanic couples immersed in 70m1 artificial saliva solution, and also specimens of four type alloy(that is, titanium, gold, silver-palladium and nickel-chromium alloy) plugs were immersed solely in 70m1 artificial sativa solution. The amount of metal elements released was observed during 21 weeks in the interval of each seven week. The electrochemical method was performed using computer-controlled potentiosta(Autostat 251. Sycopel Sicentific Ltd., U.K). The wax patterns(diameter 11.0mm, thickness,in 1.5mm) of four dental casting alloys were casted by centrifugal method and embedded in self-curing acrylic resin to be about $1.0cm^2$ of exposed surface area. Embedded specimens were polished with silicone carbide paper to #2,000, and ultrasonically cleaned. The working electrode is the specimen of four dental casting alloys, the reference electrode is a saturated calmel electrode(SCE) and the ounter electrode is made of platinum plate. In the artificial saliva solution, the potential scanning was carried out starting from-700mV(SCE) TO +1,000mV(SCE) and the scan rate was 75mV/min. Each polarization curve of alloy was recorded automatically on a logrithmic graphic paper by XY recorder. From the polarization curves of each galvanic couple, corrosion potential and corrosion rates, that is, corrosion density were compared and order of corrosion tendency was determined. From the experiments, the following results were obtained : 1. In the case of immersing titanium, gold alloy, silver-palladium alloy, and nickel-chromium alloysolely in the artificial saliva solution(group 1, 2, 3, and 4), the total amount of metal elements released was that group 4 was greater about 2, 3 times than group 3, and about 7.8 times than group 2. In the case of group 1, the amount of titanium released was not found after 8 week(p<0.001). 2. In the case of galvanic couples of titanium in contact with alloy(group 5, 6), the total amount of metal elements released of group 5 and 6 was less than that of group 7, 8, 9, and 10(p<0.05). 3. In the case of galvanic couples of titanium in contact with silver-palladium alloy(group 7, 8), the total amount of metal elements released of group 7 was greater about twice than that of group 5, and that of group 8 was about 14 times than that of group 6(p<0.05). 4. In the case of galvanic couples of titanium in contact with nickel-chromium alloy(group 9, 10), the total amount of metal elements released of group 9 and 10 was greater about 1.8-3.2 times than that of group 7 and 8, and was greater about 4.3~25 times than that of group 5 and 6(p<0.05). 5. In the effect of galvanic corrosion according to the difference of the area ratio of cathode and anode, the total amount of metal elements released was that group 5 was greater about 4 times than group 6, group 8 was greater about twice than group 7, and group 10 was greater about 1.5 times than group 9(p<0.05). 6. In the effect of galvanic corrosion according to the elasped time during 21 week in the interval of each 7 week, the amount of metal elements released was decreased markedly in the case of galvanic couples of the titanium in contact with gold alloy and silver-palladium alloy but the total amount of nickel and beryllium released was not decreased markedly in the case of galvanic couples of the titanium in contact with nickel-chromium alloy(p<0.05). 7. In the case of galvanic couples of titanium in contact with gold alloy, galvanic current was lower than any other galvanic couple. 8. In the case of galvanic couples of titanium in contact with nickel-chromium alloy, galvanic current was highest among other galvanic couples.

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Characteristics of Pd Catalysts for Methane Oxidation (메탄 산화를 위한 Pd 촉매의 특성)

  • Lee, Jin-Man;Yang, O-Bong;Kim, Chun-Yeong;Woo, Seong-Ihl
    • Applied Chemistry for Engineering
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    • v.10 no.4
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    • pp.557-562
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    • 1999
  • The reaction properties of Pd. Pd-Ce and Pd-La catalysts supported on ${\gamma}-Al_2O_3$ were investigated in the oxidation reaction of methane($CH_4$) exhausted from the compressed natural gas vehicle in a U-tube flow reactor with gas hourly space velocity of $72,000h^{-1}$. The catalysts were characterized by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), BET surface area and hydrogen chemisorption. Pd catalyst prepared by $Pd(NO_3)_2$ as a palladium precursor and calcined at $600^{\circ}C$ showed the highest activity for a methane oxidation. Catalytic activity of calcined $Pd/{\gamma}-Al_2O_3$ in which most of palladium was converted into palladium oxide species was higher than that of reduced $Pd/{\gamma}-Al_2O_3$ in which most of palladium existed in palladium metal by XRD. As increasing the number of reaction cycles in the wide range of redox, the catalytic activity of $Pd/{\gamma}-Al_2O_3$ was decreased and the highly active window became narrower. Lanthanum oxide promoted Pd catalyst, $Pd/La/{\gamma}-Al_2O_3$ showed enhanced thermal stability compared with $Pd/{\gamma}-Al_2O_3$ even after aging at $1000^{\circ}C$, which was ascribed to the role of La as a promoter to suppress the sintering of palladium metal and ${\gamma}-Al_2O_3$ support. Almost all of methane was removed by the reaction with NO at the redox ratio of 1.2 in case of oxygen excluded steam, but that activity was significantly decreased in the steam containing oxygen.

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Analysis of Resource and GHG Reduction by Recycling Palladium in Plated Spent Catalyst Solution (도금폐촉매액내 팔라듐 재자원화에 따른 자원 및 온실가스 감축량 분석)

  • Shin, Ka-Young;Lee, Seong-You;Kang, Hong-Yoon
    • Resources Recycling
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    • v.30 no.3
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    • pp.47-54
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    • 2021
  • Palladium present in colloidal-type plated spent catalyst solution that is used in electroless plating process has not been recovered but discharged as wastewater so far. Recyclig of paladium in colloidal-type plated spent catalyst solution is achieved with this study. This study presents the estimation of resource consumption and GHG emissions during the recycling and disposal of palladium in the plated spent catalyst solution using life cycle assessment. The reduction of resources and GHG are also estimated. Based on the palladium amount of 1 kg during disposal, the GHG emission amount was estimated to be 9.67E+03 kgCO2eq., and the amount of resource consumption was 3.94E+01 kgSb-eq. However, GHG emission was 1.96E+03 kgCO2eq., and the amount of resource consumption was 1.54E+01 kgSb-eq. during recycling. Considering the major substances affecting GHG emissions and amount of resource consumption, CO2 was found to significantly affect GHG emissions, accounting for 91.42% in disposal and 98.37% in recycling. The major substance affecting the amount of resource consumption was hard coal, which accounted for 40.63% in disposal and 60.73% in recycling. Upon recycling 1 kg palladium, 8,967.17 kgCO2eq. of greenhouse gas emission was reduced, while the resource consumption was reduced to 10.10 kg Sb-eq. In addition, the direct palladium resource reduction rate due to palladium recycling was 50%.

Direct Palladium-Catalyzed C-4 Arylation of Tri-substituted Furans with Aryl Chlorides: An Efficient Access to Heteroaromatics

  • Yang, Hai;Zheng, Zhishuo;Zeng, Jian;Liu, Huajie;Yi, Bing
    • Bulletin of the Korean Chemical Society
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    • v.33 no.8
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    • pp.2623-2626
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    • 2012
  • A series of functionalized furans were synthesized by way of a palladium-catalyzed coupling reaction of 2,3,5-trisubstituted furans with aryl chlorides through C-H bond cleavages at C-4 position. The feature of the reaction was facilitative preparation of furan derivatives with good functional group tolerance. All reactions gave the desired products in moderate to good yields in the presences of $BuAd_2P$ and t-BuOK in DMF at $120^{\circ}C$ after 15 h.

AN EXPERIMENTAL STUDY OF THE CYTOTOXICITY OF SILVERPALLADIUM ALLOYS UPON GINGIVAL FIBROBLAST BY MEANS OF TISSUE CULTURE (치은 섬유아세포(纖維芽細胞)에 대(對)한 은(銀)-파라디움합금(合金)의 세포독성(細胞毒性)에 관(關)한 연구(硏究))

  • Yoon, In-Tak;Choi, Boo-Byung;Kim, In-Chul
    • The Journal of Korean Academy of Prosthodontics
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    • v.21 no.1
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    • pp.9-26
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    • 1983
  • In order to investigate the biocompatibility of silver-palladium alloys, gingival fibroblast was obtained from a healthy human gingival and cultured in MEM medium with the addition of silverpalladium alloys. Four different mixture of silver-palladium alloys comprising of Ag-Pd-Au, Ag-Pd-In and Ag-Sn were tested. Results were assessed by calculating the cell multiplication rate per millimeter of medium and morphological changes in cells were also observed and noted.The obtained results were as follows; 1. Ag-Pd-Au alloy was indicated to be most biocompatible with gingival fibroblast. Also there was a decrease in cytotoxicity of the alloy as the concentration of gold increased. 2. Ag-Pd alloy showed a decrease in cell multiplication rate as compared to Ag-Pd~Au alloy. 3. Silver-palladium alloy supplemented with Indium increased the cell multiplication rate. 4. Among the alloys tested, Ag-Sn alloy was indicated to be the most cytotoxic and the least biocompatible with human gingival fibroblast.

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