• Title/Summary/Keyword: redox environment

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N3S-ligated Copper(II) Complex Catalyzed Selective Oxidation of Benzylic Alcohols to Aldehydes under Mild Reaction Conditions

  • Dharmalingam, Sivanesan;Koo, Eunhae;Yoon, Sungho;Park, Gyoosoon
    • Bulletin of the Korean Chemical Society
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    • v.35 no.3
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    • pp.715-720
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    • 2014
  • A Cu(II) complex with an three nitrogens and one sulfur coordination environment was synthesized and characterized. Its redox potential was observed at 0.483 V vs. NHE, very similar to that of a Cu-containing fungal enzyme, galactose oxidase, which catalyzes the oxidation of alcohols to corresponding aldehydes with the concomitant reduction of molecular oxygen to water. The Cu(II) complex selectively oxidizes the benzylic alcohols using TEMPO/$O_2$ under mild reaction conditions to corresponding aldehydes without forming any over-oxidation product. Moreover, the catalyst can be recovered and reused multiple times for further oxidation reactions, thus minimizing the waste generation.

Preparation and Characterization of Nickel(Ⅱ) and Copper(Ⅱ) Tetaaza Macrocyclic Complexes with Isonicotinate Ligands

  • Choi, Ki-Young;Kim, Moon-Jip;Kim, Dae-Sue;Kim, Yong-Son;Kim, Jae-Hyun;Ryu, Hai-Il;Lim, Youn-Mook;Kang, Seung-Gu;Shin, Ueon-Sang;Lee, Kyu-Chul;Hong, Choon-Pyo
    • Bulletin of the Korean Chemical Society
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    • v.23 no.8
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    • pp.1062-1066
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    • 2002
  • The complexes [Ni(L)(INT)2]${\cdot}$5H2O (1) and [Cu(L)(H2O)](Cl)(INT)${\cdot}$3H2O (2) (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18 ,07.12 ]docosane, INT = isonicotinate) have been prepared and characterized by X-ray crystallography, electronic absorption, and cyclic voltammetry. The crystal structure of 1 reveals an axially elongated octahedral geometry with two axial isonicotinate ligands. The electronic spectra, magnetic moment, and redox potentials of 1 also show a high-spin octahedral geometry. However, 2 shows that the coordination environment around the copper atom is a distorted square-pyramid with an axial water molecule. The spectra and electrochemical behaviors of 2 are also discussed.

Initial Operating Power Control of Redox Flow Battery in Offgrid 10kW ESS (독립형 10kW ESS의 레독스 플로우 배터리 초기 구동 전원 제어)

  • Choi, JM;Song, YH;Choi, ES;Eun, JM;Lee, YJ;Han, DH;Cho, YH;Choe, GH
    • Proceedings of the KIPE Conference
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    • 2013.07a
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    • pp.390-391
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    • 2013
  • This paper proposes advanced RFB PCS for islanded environment. To accommodate islanded system, power conditioning needs voltage control authority changing. RFB initial power generating method is proposed for the Islanded PCS. DC-link voltage control authority is changed to PV converter to bidirectional converter by proposed control logic. The control performance has been verified with hardware experiments.

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A Study of Structural Characteristic Control and Reaction Activity of V/TiO2 for NH3-SCR according to Preparation Method (제조방법에 따른 NH3-SCR용 V/TiO2의 구조적 특성 제어 및 반응활성 영향 연구)

  • Shin, Jung Hun;Kwon, Dong Wook;Hong, Sung Chang
    • Journal of Korean Society for Atmospheric Environment
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    • v.33 no.4
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    • pp.297-305
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    • 2017
  • In this study, the activity and structural properties of catalysts prepared by mechanochemical method under dry condition were studied. A dry milling was used as a mechanochemical method. The precursors of vanadium were $NH_4VO_3$ and $V_2O_5$. The activity and characterization of the catalysts prepared by dry milling were compared with those prepared by impregnation. In addition, the correlation between the catalytic activity and the structural characteristics was observed through XRD, Raman, and $H_2$-TPR analysis. As a result, the monomeric vanadate species exhibited excellent redox characteristics, which were confirmed to be related to the catalytic activity.

A Study on Bioremediation of Fish Farm Sediment Using CaO2 by Enhancement of Indigenous Microbial Activity (어류양식장 저질개선을 위한 과산화칼슘 투입에 의한 생태 환경변화 관찰)

  • Cho, Daechul;Bae, Hwan-Jin;Kwon, Sung-Hyun
    • Journal of Environmental Science International
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    • v.21 no.10
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    • pp.1187-1193
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    • 2012
  • The aim of this research is to enhance the bottom environment of Geoje fish farm that has been severely contaminated. Treatment of microbial agent and/or calcium oxide significantly changed that environment: in ignition loss, either treatment (25% or 21%) showed better than mixed treatment (13.2%). In COD, the oxygen releasing agent or mixed treatment reduced the index by more than 20%. In T-P and T-N, the effects of $CaO_2$ on them were overwhelming (50% or more) meanwhile that of the microbial agent on them was less than 20%. Also, $CaO_2$ influenced on the microbial flora: Desulfobvibrio thermophilus, a sulfate reducing bacterium decreased in number, considering the increase of pH and rise of redox potential. In contrast, Pseudomonas sp., Pseudoalteromonas sp., Pseudomonas aeruginosa were remarkably dominant over other species with mixed treatment as a PCA analysis confirmed it.

Removal of PCBs in Aqueous Phase in Ultraviolet (UV), Ultrasonic (US), and UV/US Processes (자외선 및 초음파 공정에 의한 수용액 상의 PCBs 분해)

  • Lee, Dukyoung;Son, Younggyu
    • Journal of Soil and Groundwater Environment
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    • v.26 no.4
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    • pp.1-7
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    • 2021
  • The removal of PCBs (Polychlorinated biphenyls) in aqueous phase was investigated in the ultraviolet (UV) process, ultrasonics (US) process and ultraviolet/ultrasonic (UV/US) process using PCB No.7 and Aroclor 1260. For PCB No.7 relatively high removal efficiency over 90% was obtained during 20 min in the UV process and UV/US process. On the other hand, lower removal efficiency of 50 - 70% was achieved for it consisted of individual congeners of PCBs containing 3~8 of chlorine atom. It was found that the dechlorination reaction (the photolytic cleavage of C-Cl bond) was considered as a main removal mechanism in the UV process while PCBs were removed by cavitation-induced radical reaction in the US process. No significant dechlorination occurred in the US process. Consequently, it was suggested that the UV process or UV/US process was applicable for the removal of PCBs in aqueous phase in terms of the removal efficiency and operation time. In addition, the application of saturating gas such as Ar and Air could be considered to control redox condition and enhance the severity of acoustic cavitation for the removal of PCBs.

The Effect of Different Membranes on the Performance of Aqueous Organic Redox Flow Battery using Methyl Viologen and TEMPOL Redox Couple (다양한 멤브레인을 적용한 메틸 바이올로겐과 템폴 활물질 기반 수계 유기 레독스 흐름 전지 성능 평가)

  • Park, GyunHo;Lee, Wonmi;Kwon, Yongchai
    • Korean Chemical Engineering Research
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    • v.57 no.6
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    • pp.868-873
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    • 2019
  • In this study, the evaluation of performance of AORFB using methyl viologen and TEMPOL as organic active materials in neutral supporting electrolyte (NaCl) with various membrane types was performed. Using methyl viologen and TEMPOL as active materials in neutral electrolyte solution, the cell voltage is 1.37V which is relatively high value for AORFB. Two types of membranes were examined for performance comparison. First, when using Nafion 117 membrane which is commercial cation exchange membrane, only the charge process occurred in the first cycle and the single cell couldn't work because of its high resistance. However, when using Fumasep anion exchange membrane (FAA-3-50) instead of Nafion 117 membrane, the result was obtained as the totally different charge-discharge graphs. When current density was $40mA{\cdot}cm^{-2}$ and cut off voltage range was from 0.55 V to 1.7 V, the charge efficiency (CE) was 97% and voltage efficiency (VE) was 78%. In addition, the discharge capacity was $1.44Ah{\cdot}L^{-1}$ which was 54% of theoretical capacity ($2.68Ah{\cdot}L^{-1}$) at $10^{th}$ cycle and the capacity loss rate was $0.0015Ah{\cdot}L^{-1}$ per cycle during 50 cycles. Through cyclic voltammetry test, it seems that this difference in the performance between the full cell using Nafion 117 membrane and Fumasep anion exchange membrane came from increasing resistance due to chemical reaction between membrane and active material, not the capacity loss due to cross-over of active material through membrane.

Assessment of Monitored Natural Attenuation as Remediation Approach for a BTEX Contaminated Site in Uiwang City (의왕시내 BTEX 오염 부지에서의 자연 정화법 이용 적합성 고찰)

  • 이민효;윤정기;박종환;이문순;강진규;이석영
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 1999.04a
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    • pp.149-156
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    • 1999
  • In the United States (U.S.), the monitored natural attenuation (MNA) approach has been used as an alternative remedial option for organic and inorganic compounds retained in soil and dissolved in groundwater. The U.S. Environmental Protection Agency (EPA) defines the MNA as“in-situ naturally-occurring processes include biodegradation, diffusion, dilution, sorption, volatilization, and/or chemical and biochemical stabilization of contaminants and reduce contaminant toxicity, mobility or volume to the levels that are protective of human health and the environment”. The Department of Soil Environment. National Institute Environmental Research (NIER) is in the process for demonstrating the MNA approach as a potential remedial option for the BTEX contaminated site in Uiwang City. The project is charactering the research site in terms of the nature and extend of contamination, biological degradation rate, and geochemical and hydrological properties. The microbial-degradation rate and effectiveness of nutrient and redox supplements will be determined through laboratory batch and column tests. The geochemical process will be monitored for determining the concentration changes of chemical species involved in the electron transfer processes that include methanogenesis, sulfate and iron reduction, denitrification, and aerobic respiration. Through field works, critical soil and hydrogeologic parameters will be acquired to simulate the effects of dispersion, advection, sorption, and biodegradation on the fate and transport of the dissolved-phase BTEX plume using Bioplume III model. The objectives of this multi-years research project are (1) to evaluate the MNA approach using the BTEX contaminated site in Uiwang City, (2) to establish a standard protocol for future application of the approach, (3) to investigate applicability of the passive approach as a secondary treatment remedy after active treatments. In this presentation, the overall picture and philosophy behind the MNA approach will be reviewed. Detailed discussions of the site characterization/monitoring plans and risk-based decision-making processes for the demonstration site will be included.

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Characteristics of Microbial Arsenic Oxidation under Denitrification Environment (미생물에 의한 탈질 과정 동안의 비소 동시 산화 특성 평가)

  • Oh, Seolran;Kim, Dong-Hun;Moon, Hee Sun
    • Journal of Soil and Groundwater Environment
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    • v.24 no.4
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    • pp.1-10
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    • 2019
  • Recently, groundwater contamination by mixed occurrence of arsenic (As) and nitrate ($NO_3{^-}$) has been a serious environmental issue all around world. In this study, we investigated the microbial As(III) oxidation characteristic under denitrification process to examine the feasibility of the microbial consortia in wetland sediment to simultaneously treat these two contaminants. The detail objectives of this study were to investigate the effects of $NO_3{^-}$ on the oxidation of As(III) in anaerobic environments and observe the microbial community change during the As oxidation under denitrification process. Results showed that the As(III) was completely and simultaneously oxidized to As(V) under denitrification process, however, it occurred to a much less extent in the absence of sediment or $NO_3{^-}$. In addition, the significant increase of As(III) oxidation rate in the presence of $NO_3{^-}$ suggested the potential of As oxidation under denitrification by indigenous microorganisms in wetland sediment. Genera Pseudogulbenkiania, and Flavisolibacter were identified as predominant microbial species driving the redox process. Conclusively, this study can provide useful information on As(III) oxidation under denitrifying environment and contribute to develop an effective technology for simultaneous removal of As(III) and $NO_3{^-}$ in groundwater.

Effect of Iron Activators on the Persulfate Oxidation of Polycyclic Aromatic Hydrocarbons (PAHs) in Contaminated Soils (다환방향족 탄화수소(PAHs) 오염토양의 과황산 산화 시 철 활성화제의 영향)

  • Choi, Jiyeon;Park, Jungdo;Shin, Won Sik
    • Journal of Soil and Groundwater Environment
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    • v.25 no.1
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    • pp.62-73
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    • 2020
  • PAHs commonly found in industrial sites such as manufactured gas plants (MGP) are potentially toxic, mutagenic and carcinogenic, and thus require immediate remediation. In-situ chemical oxidation (ISCO) is known as a highly efficient technology for soil and groundwater remediation. Among the several types of oxidants utilized in ISCO, persulfate has gained significant attention in recent years. Peroxydisulfate ion (S2O82-) is a strong oxidant with very high redox potential (E0 = 2.01 V). When mixed with Fe2+, it is capable of forming the sulfate radical (SO4) that has an even higher redox potential (E0 = 2.6 V). In this study, the influence of various iron activators on the persulfate oxidation of PAHs in contaminated soils was investigated. Several iron sources such as ferrous sulfate (FeSO4), ferrous sulfide (FeS) and zero-valent iron (Fe(0)) were tested as a persulfate activator. Acenaphthene (ANE), dibenzofuran (DBF) and fluorene (FLE) were selected as model compounds because they were the dominant PAHs found in the field-contaminated soil collected from a MGP site. Oxidation kinetics of these PAHs in an artificially contaminated soil and the PAH-contaminated field soil were investigated. For all soils, Fe(0) was the most effective iron activator. The maximum PAHs removal rate in Fe(0)-mediated reactions was 92.7% for ANE, 83.0% for FLE, and 59.3% for DBF in the artificially contaminated soil, while the removal rate of total PAHs was 72.7% in the field-contaminated soil. To promote the iron activator effect, the effects of hydroxylamine as a reducing agent on reduction of Fe3+ to Fe2+, and EDTA and pyrophosphate as chelating agents on iron stabilization in persulfate oxidation were also investigated. As hydroxylamine and chelating agents (EDTA, pyrophosphate) dosage increased, the individual PAH removal rate in the artificially contaminated soil and the total PAHs removal rate in the field-contaminated soil increased.