• Title/Summary/Keyword: copper complexes

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Self-assembly Coordination Compounds of Cu(II), Zn(II) and Ag(I) with btp Ligands (btp = 2,6-bis(N'-1,2,4-triazolyl)pyridine):Counteranion Effects

  • Kim, Cheal;Kim, Sung-Jin;Kim, Young-Mee
    • Korean Journal of Crystallography
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    • v.16 no.2
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    • pp.107-127
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    • 2005
  • Five Cu(II) compounds were obtained from different copper salts with btp ligands, and their structures were determined by X-ray crystallography. The structure of coordination polymer 2 contains btp-bridged tetranuclear Cu(II) units weakly connected by nitrate ions, and the structure of a discrete Cu(II) molecule 1 contains acetates and btp ligands. With perchlorate anions, two btp ligands bridge Cu(II) ions to form a double zigzag chain 3, while a single zigzag chain 4 is created with sulfate anions. The reaction of $Cu(NO_{3})_{2}$ containing $NH_{4}PF_{6}$ with btp ligands also produced a polymeric compound 5 containing $Cu(H_{2}O)_{2}^{2+}$ and $Cu(NO_{3})_{2}$ units alternatively bridged by btp ligands with H-bonds between copper bonded water and nitrate oxygen atoms. Five Zn(II) compounds were obtained from different zinc salts with btp ligands, and the structures of polymeric compounds (6, 7 and 8) and monomeric compounds (9 and 10) were determined by X-ray crystallography. With nitrate, chloride and bromide anions, btp ligands bridge Zn(II) ions to form polymeric compounds (6, 7 and 8), but btp ligands coordinate to a Zn(II) ion to form monomeric complexes (9 and 10) with $PF_{6}^{-}$ and perchlorate anions. Four silver salts and btp ligands produced two kinds of structures, dinuclear 20-membered rings and one-dimensional zigzag chain depending on different anions. For $ClO_{4}^{-}$ and OTf anions, weak interactions between Ag(I) and anions make dinuclear 20-membered rings construct polymeric compounds (11 and 13). For $PF_{6}^{-}$ anion, there are also weak interactions between Ag(I) and $F(PF_{6}^{-})(12)$, but they do not construct a polymeric compound. For $O_{2}CCF_{3}^{-}$ anion, btp ligands bridge Ag(I) atoms to make one-dimensional zigzag chain (14), and there are also interactions between Ag(I) and anions.

Electrocatalytic Reduction of CO2 by Copper (II) Cyclam Derivatives

  • Kang, Sung-Jin;Dale, Ajit;Sarkar, Swarbhanu;Yoo, Jeongsoo;Lee, Hochun
    • Journal of Electrochemical Science and Technology
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    • v.6 no.3
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    • pp.106-110
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    • 2015
  • This study investigates Cu(II) complexes of cyclam, propylene cross-bridged cyclam (PCB-cyclam), and propylene cross-bridged cyclam diacetate (PCB-TE2A) as homogeneous electrocatalysts for CO2 reduction in comparison with Ni(II)-cyclam. It is found that Cu(II)-cyclam can catalyze CO2 reduction at the potential close to its thermodynamic value (0.75 V vs. Ag/AgCl) in tris-HCl buffer (pH 8.45) on a glassy carbon electrode. Cu(II)-cyclam, however, suffers from severe demetalation due to the insufficient stability of Cu(I)-cyclam. Cu(II)-PCB-cyclam and Cu(II)-PCB-TE2A are revealed to exhibit much less demetalation behavior, but poor CO2 reduction activities as well. The inferior electrocatalytic ability of Cu(II)-PCB-cyclam is ascribed to its redox potential that is too high for CO2 reduction, and that of Cu(II)-PCB-TE2A to the steric hindrance preventing facile contact with CO2 molecules. This study suggests that in addition to the redox potential and chemical stability, the stereochemical aspect has to be considered in designing efficient electrocatalysts for CO2 reduction.

Efficient use of ferrate(VI) for the remediation of wastewater contaminated with metal complexes

  • Sailo, Lalsaimawia;Pachuau, Lalramnghaki;Yang, Jae Kyu;Lee, Seung Mok;Tiwari, Diwakar
    • Environmental Engineering Research
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    • v.20 no.1
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    • pp.89-97
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    • 2015
  • Remediation of wastewater contaminated with metal(II)-complexed species (Cu(II)-NTA (NTA: nitrilotriacetic acid), Cu(II)-EDTA (EDTA: ethylenediamine tetraacetic acid) and Cd(II)-EDTA is attempted using the potential applicability of ferrate(VI). Kinetics of pollutant degradation is obtained with the removal of ferrate(VI) studied at wide range of pH (8.0-10.0) and the concentration of metal(II)-complexed species (0.3 to 15.0 mmol/L) employing a constant dose of ferrate(VI) i.e., 1.0 mmol/L. Pseudo-first-order and pseudo-second-order rate constants were obtained in the reduction of ferrate(VI) which was then employed to obtain the overall rate constants of the pollutant degradation. The mineralization of NTA and EDTA was obtained with the change in TOC (total organic carbon) values collected by the ferrate(VI) treated pollutant samples. Decrease in pH and molar pollutant concentrations was greatly favored the percent mineralization of NTA or EDTA by the ferrate(VI) treatment. The treated pollutant samples were filtered and subjected for AAS (atomic absorption spectrophotometric) analysis to assess the simultaneous removal of copper and cadmium from aqueous solutions at the studied pH as well at the elevated pH 12.0. Results show that an enhanced removal of cadmium or copper was achieved at pH 12.0. Overall, ferrate(VI) possesses multifunctional application in wastewater treatment as it oxidizes the degradable impurities and removes metallic impurities by coagulation process.

Adsorption Characteristics of Ammonia Complex of Copper(II) on Activated Carbon (활성탄에 의한 구리(II) 암모니아 착염이온의 흡착 특성)

  • Hong, Wan-Hae;Kim, Jung-Gyu;Na, Sang-Kwon
    • Applied Chemistry for Engineering
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    • v.8 no.1
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    • pp.23-28
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    • 1997
  • The adsorption characteristics of ammonia-Cu(II) complex on activated carbon were studied. Firstly, the specific surface area of the activated carbon was measured by using the BET adsorption apparatus. Secondly, the characteristics of the removal copper(II) ion from aqueous ammonia solution by forming a complex with ammonia and then by the adsorption of the complex on the activated carbon were studied. It was found that the specific surface area increases with decreasing the mesh number of the activated carbon, and the optimum pH for the adsorption of the Cu(II) ion on she activated carbon was found to be approximately 6. It was also found that the adsorbed Cu(II)-ammonia complexes on the activated carbon in the aqueous ammonia solution have two types, depending on the concentration of the solution ; i.e. $[Cu(NH_3){_2}]^{2+}$and $[Cu(NH_3){_3}]^{2+}$ for $2.25{\times}10^{-4}(mol/{\ell})$and $2.25{\times}10^{-3}(mol/{\ell})$, respectively.

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Studies on Amidoximated Acrylic Fiber(I) -Amidoximation and Adsorption Capacity to Transition Metals - (아크릴 섬유의 아미도옥심화에 관한 연구(I) -아미도옥심 반응과 천이금속의 흡착능-)

  • Chin, Young Gil;Kim, Kyu Beom
    • Textile Coloration and Finishing
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    • v.8 no.6
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    • pp.40-46
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    • 1996
  • In order to investigate a practical application of fibrous absorbents to transition metals such as copper, nickel, cobalt, chrome, and iron, amidoximated fiber as a particular class of solid chelate agents were prepared from acrylic fibers treatment with hydroxylamine. The adsorption mechanisms of metal ions onto amidoximated acrylic fibers and their complexes were studied. Amidoximation of acrylic fiber with hydroxylamine is found to be first-order reaction, followed by the disappearance of infrared adsorption peaks due to nitrile groups of acrylic fibers. The uptake of metal ions onto amidoximated acrylic fiber is increased with temperature raising and the adsorption is also depended on pH of the soiutions. About 70% of metal ions can be recovered from aqueous solutions of Ni(II), Co(II), Cr(III), and Fe(II) on the concentration below 5x 10$^$^{-4}$ in the range of pH 2.1~10.0. Transition metals are adsorbed to form complex with amidoxime group by the ligand sites such as C=N, NH, NO, NHOH.OH.

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Comparisons on Relative Growth of Red Pine, Black Pine and Pitch Pine by Means of Multiple Regression (다중회귀분석법에 의한 소나무, 곰솔 및 리기다소나무의 상대성장 비교)

  • Park, Man-Choon;Lee, Yun-Keun;Choi, Kee-Ryong
    • Journal of Environmental Science International
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    • v.19 no.3
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    • pp.305-312
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    • 2010
  • The purpose of this study is to compare the relative growth of annual ring width of red pine(Pinus densiflora), black pine(Pinus thunbergii) and pitch pine(Pinus rigida) by means of multiple regression method according to Graybill hypothesis. The obtained results are as follows. 1. The changes of rainfall have affected to tree growth during the periods of 1975 through 1978. 2. Among these pine trees, red pine was mostly influenced by environmental factors. 3. The growth of annual ring width was sensitively responded to the changes of rainfall and air temperature. 4. Among the heavy metals analyzed, the concentrations(ppm) of Lead(Pb) and Copper(Cu) were negatively effected on the growth of annual ring width of pine trees. 5. The analytical technique of annual ring width may be useful for estimation of the pollution in forest areas near industrial complexes.

Realistic adsorption behaviors of the copper onto the functionalized CNTs

  • Park, Mi-Na;Kim, Byeong-Hyeon;Lee, Gwang-Ryeol
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.02a
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    • pp.476-476
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    • 2011
  • Introduction of CNTs into a metal matrix has been considered to improve the mechanical properties of the metal matrix. However, the binding energy between metals and pristine CNTs wall is known to be so small that the interfacial slip between CNTs and the matrix occurs at a relatively low external stress. The interfacial strength between CNT and metal matrix is thus one of the key factors for successful development of the CNT/metal composites. Defective or functionalized CNT has been considered to enhance the interfacial strength of nanocomposites. In the present work, we design the various realistic hybrid structures of the single wall CNT/Cu complexes and characterize the interaction between single wall CNTs and Cu nano-particle and Cu13 cluster using first principle calculations. The characteristics of functionalized CNTs with various surface functional groups, such as -COOH, -OH, and -O interacting with Cu are investigated. We found that the binding energy can be enhanced by the surface functional group including oxygen since the oxygen atom can mediate and reinforce the interaction between carbon and Cu. These results strongly support the recent experimental work which suggested the oxygen on the interface playing an important role in the excellent mechanical properties of the CNT/Cu composite.

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Extraction of Water-Soluble Porphyrin and Metalloporphyrins into Acetonitrile by Salting-out

  • Tabata, Masaaki;Kumamoto, Midori
    • Analytical Science and Technology
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    • v.8 no.4
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    • pp.511-517
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    • 1995
  • A cationic water soluble porphyrin (5,10,15,20-tetrakis (l-methyl-pyridinium-4-yl)porphyrin, $H_2tmpyp^{4+}$) and its metalloporphyrins (MP) were easily extracted into acetonitrile separated by addition of sodium chloride ($4mol\;dm^{-3}$) in the presence of sodium perchlorate, where M denotes $Zn^{2+}$, $Cu^{2+}$, $Co^{3+}$, $Fe^{3+}$, and $Mn^{3+}$ and $P^{2-}$ is porphyrinate ion. The extracted ion-pair complexes were completely dissociated to $[MP(ClO_4)_3]^+$, and $[MP(ClO_4)_2]^{2+}$. The extraction and the dissociation constants were determined by taking into account of the partition constant of sodium perchlorate ($K_D=1.82{\pm}0.01$). The chemical properties of the separated acetonitrile phase as $E_{T(30)}$ and $D_{II,I}$ were determined and compared with other water miscible solvents (acetone, actonitrile, 1,4-dioxane, tetrahydrofuran, 1-propanol and 2-propanol). Furthermore, a sensitive and selective method was proposed for the determination of a subnanogram amount of copper(II) in natural water samples by using the present salting-out method and the porphyrins.

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Determination of Mercury(II) Using Nafion-EDTA-Modified Glassy Carbon Electrodes (Nafion-EDTA가 수식된 유리탄소전극을 이용한 수은(II)의 측정)

  • 정근호;박찬주;박율희;이지영
    • Journal of Environmental Health Sciences
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    • v.26 no.4
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    • pp.110-114
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    • 2000
  • Determination of mercury(II) using Nafion-EDTA-modified glassy carbon electrodes is proposed. it is based on the chemical reactivity of an immobilized modifier, Nafion-EDTA. Differential pulse voltammetry is employed, and the oxidation of complexes, at +0.43V vs. Ag/AgCl, is observed. For a 5-min preconcentration period, a linear calibration curve is obtained for mercury(II) concentrations ranging from 1.0$\times$ 10$^{-8}$ to 1.0$\times$10$^{-6}$ M. Further, when an approximate amount of copper(II) is added to the test solution, We demonstrate that at a preconcentration time of 5 min the Nafion-EDTA-modified glassy carbon electrode has a dynamic range of 2 orders of magnitude(from 10$^{-10}$ to 10$^{-8}$ M) and the detection limit is as low as 0.5$\times$ 10$^{-10}$ M(0.01 ppb). This method is applied to the determination of mercury(II) in sea water(4.0$\times$10$^{-10}$ M, 0.08ppb). The result agrees satisfactorily with the value(below 0.1 ppb) measured by using ICP/MS.

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The Treatment of Heavy Metal-cyanide Complexes Wastewater by $Zn^{+2}/Fe^{+2}$ Ion and Coprecipitation in Practical Plant(I) (아연백법 및 공침공정을 이용한 복합 중금속-시안착염 폐수의 현장처리(I))

  • Lee, Jong-Cheul;Kang, Ik-Joong
    • Journal of Korean Society of Environmental Engineers
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    • v.29 no.12
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    • pp.1381-1389
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    • 2007
  • Wastewater discharged by industrial activities of metal finishing and electroplating units is often contaminated by a variety of toxic or otherwise harmful substances which have a negative effects on the water environment. The treatment method of heavy metal-cyanide complexes wastewater by alkaline chlorination have already well-known($1^{st}$ Oxidation: pH 10, reaction time 30 min, ORP 350 mV, $2^{nd}$ Oxidation: ORP 650 mV). In this case, the efficiency for the removal of ferro/ferri cyanide by this general alkaline chlorination is very high as 99%. But the permissible limit of Korean waste-water discharge couldn't be satisfied. The initial concentration of cyanide was 374 mg/L(the Korean permissible limit of cyanide is 1.0 mg/L max.). So a particular focus was given to the treatment of heavy metal-cyanide complexes wastewater by $Zn^{+2}/Fe^{+2}$ ion and coprecipitation after alkaline chlorination. And we could meet the Korean permissible limit of cyanide(the final concentration of cyanide: 0.30 mg/L) by $Zn^{+2}/Fe^{+2}$ ion and coprecipitation(reaction time: 30 min, pH: 8.0, rpm: 240). The removal of Chromium ion by reduction(pH: 2.0 max, ORP: 250 mV) and the precipitation of metal hydroxide(pH: 9.5) is treated as 99% of removal efficiency. The removal of Copper and Nickel ion has been treated by $Na_2S$ coagulation-flocculation as 99% min of the efficiency(pH: $9.09\sim10.0$, dosage of $Na_2S:0.5\sim3.0$ mol). It is important to note that the removal of ferro/ferri cyanide of heavy metal-cyanide complexes wastewater should be employed by $Zn^{+2}/Fe^{+2}$ ion and coprecipitation as well as the alkaline chlorination for the Korean permissible limit of waste-water discharge.