• Title/Summary/Keyword: metal complex

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Selective Dimerization and Cyclotrimerization of Phenylacetylene with Rhodium and Iridium Complexes

  • Chin, Chong-Shik;Won, Gyong-Shik;Song, Joong-Ho
    • Bulletin of the Korean Chemical Society
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    • v.15 no.11
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    • pp.961-966
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    • 1994
  • Oligomerization of phenylacetylene is catalyzed by $Rh(ClO_4)(CO)(PPh_3)_2$ (Rh-1), $[Rh(CO)(PPh_3)_3]ClO_4$ (Rh-2), $[Rh(COD)L_2]ClO_4 (L_2=(PPh_3)_2$, Rh-3; $(PPh_3)(PhCN)$, Rh-4; $(PhCN)_2$, Rh-5), $[Rh(C_3H_5)(Cl)(CO)(SbPh_3)_2]ClO_4$ (Rh-6), $[Ir(COD)L_2]ClO_4 (L_2=(PPh_3)_2$, $Ir-1; (PPh_3)(PhCN)$, $Ir-2; (PhCN)_2$, Ir-3; (AsPh_3)(PhCN)$, $Ir-4; Ph_2PCH_2CH_2PPh_2$, Ir-5; COD, Ir-6 and 2,2'-dipyridyl, Ir-7), $Ir(ClO_4)(CO)(PPh_3)_2$, $Ir-8, [Ir(PhCN)(CO)(PPh_3)_2]ClO_4$, Ir-9 to produce dimerization products, 1,3-diphenylbut-1-yn-3-ene, 1, (E)-1,4-diphenylbut-1-yn-3-ene, 2 and (Z)-1,4-diphenylbut-1-yn-3-ene, 3, and cyclotrimerization products, 1,3,5-triphenylbenzene, 4 and 1,2,4-triphenylbenzene, 5. Product distribution of the oligomers varies depending on various factors such as the nature of catalysts, reaction temperature, counter anions and excess ligand present in the reaction mixtures. Increasing reaction temperature in general increases the yield of the cyclotrimerization products. Exclusive production of dimer 1 and trimer 4 can be obtained with Ir-1 at 0 $^{\circ}$C and with Ir-2 in the presence of excess PhCN (or $CH_3CN$) at 50 $^{\circ}$C, respectively. Dimer 2 (up to 81%) and trimer 5 (up to 98%) are selectively produced with Rh-1 at 50 and 100 $^{\circ}$C respectively. Production of 3 is selectively increased up to 85% by using $PF_6$- salt of $[Ir(COD)(PPh_3)_2]$+ at 25 $^{\circ}$C. Addition of $CH_3I$ to Rh-1 produces $CH_3PPh_3^+I-$ and increases the rate of oligomerization(disappearance of phenylacetylene). Among the metal compounds investigated in this study, Ir-1 catalyzes most rapidly the oligomerization where the catalytically active species seems to contain lr(PPh3)2 moiety. The stoichiometric reaction of phenylacetylene wth Ir-9 at 25 $^{\circ}$C quantitatively produces hydridophenyl-ethynyl iridium(III) complex, $[lr(H)(C{\equiv}CPh)(PhCN)(CO)(PPh_3)_2]ClO_4$ (Ir-11), which seems to be an intermediate for the oligomerization.

Feasibility Study of Different Biochars as Adsorbent for Cadmium and Lead

  • Kim, In Ja;Kim, Rog-Young;Kim, Ji In;Kim, Hyoung Seop;Noh, Hoe-Jung;Kim, Tae Seung;Yoon, Jeong-Ki;Park, Gyoung-Hun;Ok, Yong Sik;Jung, Hyun-Sung
    • Korean Journal of Soil Science and Fertilizer
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    • v.48 no.5
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    • pp.332-339
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    • 2015
  • The objective of this study was to evaluate the effectiveness of different biochars on the removal of heavy metals from aqueous media. The experiment was carried out in aqueous solutions containing $200mg\;CdL^{-1}$ or $200mg\;PbL^{-1}$ using two different biochars derived from soybean stover and orange peel (20 mg Cd or $Pbg^{-1}$ biochar). After shaking for 24 hours, biochars were filtered out, and Cd and Pb in the filtrate were analyzed by flame atomic absorption spectrophotometer (FAAS). In order to provide information regarding metal binding strength on biochars, sequential extraction was performed by modified SM&T (formerly BCR). The results showed that 70~100% of initially added Cd and Pb was adsorbed on biochars and removed from aqueous solution. The removal rate of Pb (95%, 100%) was higher than that of Cd (70%, 91%). In the case of Cd, orange peel derived biochar (91%) showed higher adsorption rate than soybean stover derived biochar (70%). Cd was adsorbed on the biochar mainly in exchangeable and carbonates fraction (1st phase). In contrast, Pb was adsorbed on it mainly in the form of Fe-Mn oxides and residual fraction (2nd and 4th phase). The existence of Cd and Pb as a form of surface-precipitated complex was also observed on the surfaces of biochars detected by field emission scanning electron microscope (FESEM) and energy dispersive X-ray spectrometer (EDAX).

Leaching Behavior of Heavy Metals from an Ore Containing High Concentration as Utilizing Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans (Acidithiobacillus ferrooxidans와 Acidithiobacillus thiooxidans를 활용한 고농도 비소 함유 광석 내 중금속 용출 거동 연구)

  • Kim, Gahee;Kim, Rina;Kim, Kwanho;You, Kwang-suk
    • Resources Recycling
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    • v.30 no.2
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    • pp.14-23
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    • 2021
  • To investigate the potential for leaching of heavy metals by bacteria from ores stacked on actual mining sites, leaching tests of a complex metallic ore (Pb-Zn-As ore) were conducted over 60 days using acidophile bacteria Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans under initial acidic conditions. Initially, a small amount of heavy metals was leached due to the initial acidic conditions. After 20 days, when A. thiooxidans in the reactor was adapted to the ore, the amount of leached heavy metals rapidly increased; the concentrations of leached arsenic, iron, and zinc reached a maximum of 2800, 3700, and 2500 mg/L, respectively. On the other hand, in the presence of A. ferrooxidans or in the control test without bacteria, heavy metals, except zinc, were barely detected in leaching. Through this study, it was confirmed that (i) bacteria could leach heavy metals at mining sites under acidic conditions and (ii) leaching of heavy metals from a high arsenic-containing ore by A. thiooxidans was more significant than that by A. ferrooxidans.

Effect of Temperature on Growth of Tin Oxide Nanostructures (산화주석 나노구조물의 성장에서 기판 온도의 효과)

  • Kim, Mee-Ree;Kim, Ki-Chul
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.20 no.4
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    • pp.497-502
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    • 2019
  • Metal oxide nanostructures are promising materials for advanced applications, such as high sensitive gas sensors, and high capacitance lithium-ion batteries. In this study, tin oxide (SnO) nanostructures were grown on a Si wafer substrate using a two-zone horizontal furnace system for a various substrate temperatures. The raw material of tin dioxide ($SnO_2$) powder was vaporized at $1070^{\circ}C$ in an alumina crucible. High purity Ar gas, as a carrier gas, was flown with a flow rate of 1000 standard cubic centimeters per minute. The SnO nanostructures were grown on a Si substrate at $350{\sim}450^{\circ}C$ under 545 Pa for 30 minutes. The surface morphology of the as-grown SnO nanostructures on Si substrate was characterized by field-emission scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM). Raman spectroscopy was used to confirm the phase of the as-grown SnO nanostructures. As the results, the as-grown tin oxide nanostructures exhibited a pure tin monoxide phase. As the substrate temperature was increased from $350^{\circ}C$ to $424^{\circ}C$, the thickness and grain size of the SnO nanostructures were increased. The SnO nanostructures grown at $450^{\circ}C$ exhibited complex polycrystalline structures, whereas the SnO nanostructures grown at $350^{\circ}C$ to $424^{\circ}C$ exhibited simple grain structures parallel to the substrate.

Public Cognition and Information Acquisition Route for Heavy Metals and Organic Solvents in General Population of Korea (한국인의 중금속과 유기용제에 대한 인식도와 정보취득 경로)

  • Lee, Chae Kwan
    • Journal of Korean Society of Occupational and Environmental Hygiene
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    • v.31 no.1
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    • pp.73-82
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    • 2021
  • Objectives: This study aimed to investigate the public cognition and information acquisition route for heavy metals and organic solvents in the general population in order to provide information for the development of public relations materials. Methods: The study was carried out by questionnaire from January to March 2011 by an interview with trained surveyors. There were 700 participants, divided by gender and age. A questionnaire was issued consisting of subjective and objective cognition evaluation items and questions about information acquisition route and preferred information acquisition route for six heavy metals and five organic solvents. Data were expressed as a percentage using the SPSS 23.0 software package. Result: For heavy metals, subjective and objective cognition degrees were higher in the order of lead, mercury, cadmium, and arsenic. They were higher among males than females, and in adults compared to school-age subjects. For organic solvents, both cognition degrees were high in the order of acetone, benzene, and formaldehyde. However, cognition degree by gender and age showed a complex pattern. As a response to information acquisition route, broadcast media had the highest in all ages and genders, followed by word of mouth from neighbors in elementary school children, school education or expert lectures in middle and high school students up to people in their 30s, and print media among those in their 40s to over 60s. There was no difference in the order by gender. As a response to preference for information acquisition route, broadcast media also proved the highest in all ages and genders, followed by school education or professional lectures among those in elementary school and over their 60s, and the internet in other age groups. Females preferred school education or expert lectures and word of mouth from neighbors, while males preferred the internet. In the case of the internet, the ranking was higher for preferred information acquisition route compared with the ranking for information acquisition route. Conclusions: This data on cognition degree, information acquisition route, and preferred information acquisition route according to gender and age can provide basic data for the development of educational and promotional materials for heavy metals and organic solvents exposure management.

Application of Ferrate (VI) for Selective Removal of Cyanide from Plated Wastewater (도금폐수 중 시안(CN)의 선택적 제거를 위한 Ferrate (VI) 적용)

  • Yang, Seung-Hyun;Kim, Younghee
    • Clean Technology
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    • v.27 no.2
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    • pp.168-173
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    • 2021
  • The treatment of plated wastewater is subject to various and complex processes depending on the pH, heavy metal, and cyanide content of the wastewater. Alkali chlorine treatment using NaOCl is commonly used for cyanide treatment. However, if ammonia and cyanide are present simultaneously, NaOCl is consumed excessively to treat ammonia. To solve this problem, this study investigated 1) the consumption of NaOCl according to ammonia concentration in the alkaline chlorine method and 2) whether ferrate (VI) could selectively treat the cyanide. Experiments using simulated wastewater showed that the higher the ammonia concentration, the lower the cyanide removal rate, and the linear increase in NaOCl consumption according to the ammonia concentration. Removal of cyanide using ferrate (VI) confirmed the removal of cyanide regardless of ammonia concentration. Moreover, the removal rate of ammonia was low, so it was confirmed that the ferrate (VI) selectively eliminated the cyanide. The cyanide removal efficiency of ferrate (VI) was higher with lower pH and showed more than 99% regardless of the ferrate (VI) injection amount. The actual application to plated wastewater showed a high removal ratio of over 99% when the input mole ratio of ferrate (VI) and cyanide was 1:1, consistent with the molarity of the stoichiometry reaction method, which selectively removes cyanide from actual wastewater containing ammonia and other pollutants like the result of simulated wastewater.

Evaluation of 3D Printing Filaments for Radiation Shielding using High Density Polyethylene and Bismuth (고밀도 폴리에틸렌과 비스무트를 이용한 3D 프린팅용 방사선 복합필라멘트 개발 및 차폐능력 평가)

  • Park, Ki-Seok;Kim, Dong-Hyun
    • Journal of the Korean Society of Radiology
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    • v.16 no.3
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    • pp.233-240
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    • 2022
  • Research on the presence or absence of radiation shielding for FDM-type filaments has recently begun to be studied, but filaments with shielding capabilities are not sold in Korea, and not studies yet. Therefore, in this research, we will use HDPE (High Density Polyethylene) as a base material, select bismuth as a reinforcing material to manufacture a composite filament, evaluate the shielding ability, and provide basic data for the development of a radiation shielding composite material using 3D printing.A filament is produced by mixing Bismuth with an effective atomic number 83 with HDPE of PE series and adjusting the content of Bismuth to 20% wt, 30% wt, 40% wt. Compounded filaments were evaluated for their physical properties and shielding capabilities by ASTM evaluation methods. As the bismuth content increases, the density, weight, and tensile strength increase, and the shielding capacity is confirmed to be excellent. As a result of the radiation shielding capacity evaluation, it was confirmed that HDPE (80%) + Bi (20%) showed a shielding rate of 82% at 60 kV and a shielding rate of up to 94% or more at 40% bismuth content. In this study, we confirmed that it was possible to produce a radiation shield that is lighter than the metal particle-containing filaments. Furthermore, that have been shield radiation by using HDPE + Bi filaments, and radiation in the medical and radiation industries. The possibility of using it as a shielding complex was confirmed.

Estimation of Spatial Distribution Using the Gaussian Mixture Model with Multivariate Geoscience Data (다변량 지구과학 데이터와 가우시안 혼합 모델을 이용한 공간 분포 추정)

  • Kim, Ho-Rim;Yu, Soonyoung;Yun, Seong-Taek;Kim, Kyoung-Ho;Lee, Goon-Taek;Lee, Jeong-Ho;Heo, Chul-Ho;Ryu, Dong-Woo
    • Economic and Environmental Geology
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    • v.55 no.4
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    • pp.353-366
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    • 2022
  • Spatial estimation of geoscience data (geo-data) is challenging due to spatial heterogeneity, data scarcity, and high dimensionality. A novel spatial estimation method is needed to consider the characteristics of geo-data. In this study, we proposed the application of Gaussian Mixture Model (GMM) among machine learning algorithms with multivariate data for robust spatial predictions. The performance of the proposed approach was tested through soil chemical concentration data from a former smelting area. The concentrations of As and Pb determined by ex-situ ICP-AES were the primary variables to be interpolated, while the other metal concentrations by ICP-AES and all data determined by in-situ portable X-ray fluorescence (PXRF) were used as auxiliary variables in GMM and ordinary cokriging (OCK). Among the multidimensional auxiliary variables, important variables were selected using a variable selection method based on the random forest. The results of GMM with important multivariate auxiliary data decreased the root mean-squared error (RMSE) down to 0.11 for As and 0.33 for Pb and increased the correlations (r) up to 0.31 for As and 0.46 for Pb compared to those from ordinary kriging and OCK using univariate or bivariate data. The use of GMM improved the performance of spatial interpretation of anthropogenic metals in soil. The multivariate spatial approach can be applied to understand complex and heterogeneous geological and geochemical features.

A Study on the Comparison of Areas Near Gunsan according to the Revision of the National Air Pollutant Emissions (CAPSS) in 2020 (국가대기오염물질 배출량(CAPSS)의 2020년 산정 방법 개정에 따른 군산 인근지역 비교에 관한 연구)

  • Sang-Hun Park;Seong-Cheon Kim
    • Journal of Environmental Health Sciences
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    • v.49 no.4
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    • pp.190-200
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    • 2023
  • Background: Gunsan has been constantly affected by pollutants generated by the Saemangeum development and the construction industry since the completion of the Saemangeum seawall on April 27, 2010. However, there are limitations to its study, such as taking into consideration weather conditions, geographical factors, and foreign inflows. Objectives: In this study, we compared the Existing-CAPSS emissions of Gunsan with Recalculated-CAPSS emissions data to analyze the differences in emissions characteristics by year (2016~2019). Methods: Using Existing data on CAPSS emissions (2016~2019) and Recalculated-CAPSS emissions (2016~2019) for Gunsan, which were Recalculated following the improvement of emissions calculations for 2020, we organized CO, NOX, SOX, PM10, VOCS, and NH3 emissions by substance and investigated the differences and characteristics of the Recalculated emissions by year. Results: For Re-CO and Re-PM10, the emission characteristics of CO were examined as energy industry combustion and PM10 emission characteristics were examined as ship cargo from non-road transportation sources, as ship leisure sources were excluded from non-road transportation source emissions. Conclusions: Comparing the emissions of Existing-CAPSS and Recalculated-CAPSS in Gunsan, the emissions of Recalculated-CAPSS by substance decreased by 39.76% for CO, 9.98% for PM10, 5.53% for VOCS, and 9.24% for NH3, while Re-NOX increased by 2.86% and Re-SOX increased by 1.97%. On the other hand, when comparing the emissions characteristics of Existing-CAPSS and Recalculated-CAPSS in Gunsan, Jeonju, and Iksan, the emission characteristics of Re-NOX, Re-SOX, Re-VOCS and Re-NH3 were similar to those of Ex-NOX, Ex-SOX, Ex-VOCS, and Ex-NH3. As such, Gunsan, Iksan, and Jeonju, showed differences in the comparison of different emission characteristics due to the geographical characteristics of the region (population, area, topography, weather factors) and the characteristics of the industrial complex (metal, petrochemical).

Genetic Environments at the Ssangjeon Tungsten-bearing Hydrothermal Vein Deposit (쌍전 함 텅스텐 열수 맥상광상의 생성환경)

  • Sunjin Lee;Sang-Hoon Choi
    • Economic and Environmental Geology
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    • v.55 no.6
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    • pp.689-699
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    • 2022
  • The Ssangjeon tungsten deposit is located within the Yeongnam Massif. Within the area a number of hydrothermal quartz veins were formed by narrow open-space filling of parallel and subparallel fractures in the metasedimentary rocks as Wonnam formation, Buncheon granite gneiss, amphibolite and/or pegmatite. Mineral paragenesis can be divided into two stages (stage I, ore-bearing quartz vein; stage II, barren quartz vein) by major tectonic fracturing. Stage I, at which the precipitation of major ore minerals occurred, is further divided into three substages (early, middle and late) with paragenetic time based on minor fractures and discernible mineral assemblages: early, marked by deposition of arsenopyrite with pyrite; middle, characterized by introduction of wolframite and scheelite with Ti-Fe-bearing oxides and base-metal sulfides; late, marked by Bi-sulfides. Fluid inclusion data show that stage I ore mineralization was deposited between initial high temperatures (≥370℃) and later lower temperatures (≈170℃) from H2O-CO2-NaCl fluids with salinities between 18.5 to 0.2 equiv. wt. % NaCl of Ssangjeon hydrothermal system. The relationship between salinity and homogenization temperature indicates a complex history of boiling, fluid unmixing (CO2 effervescence), cooling and dilution via influx of cooler, more dilute meteoric waters over the temperature range ≥370℃ to ≈170℃. Changes in stage I vein mineralogy reflect decreasing temperature and fugacity of sulfur by evolution of the Ssangjeon hydrothermal system with increasing paragenetic time.