• Title/Summary/Keyword: Redox behavior

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Synthesis of Electroactive Polythiophene Derivatives and Its Application for Biointerface (I) (전기적 활성을 갖는 폴리티오펜 유도체들의 합성과 생체계면에의 응용 (I))

  • 정선형;배진영;김지흥;정동준
    • Polymer(Korea)
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    • v.26 no.1
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    • pp.28-36
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    • 2002
  • In this study, we synthesized novel thiophene derivatives by the protection of the carboxyl group of 3-thiophene acetic acid with differently substituted benzyl groups. While 3-thiophene acetic acid is not electro-polymerizable, the modified monomers can be easily electro-oxidized to form stable electroactive polymers. The protecting groups can be easily removed in the solid state and the desired reactive carboxyl group can be introduced on the polymer surface. SEM observations show that obtained polymer films show a very good film surface and homogeneous morphology on the Pt electrode. After introduction of macromonomer, FT-IR spectrum shows new absorption bands at 1650 and $1550 cm^{-1}$, which is consistent with the formation of an amide bond. Electroactivity measurements were examined by cyclic voltammogram(CV). These polymers showed the characteristic electrochemical behavior of poly(3-alkylthiophene)s with reversible redox transition in the range of 0.7-0.9 V.

Use of hybrid materials in the trace determination of As(V) from aqueous solutions: An electrochemical study

  • Tiwari, Diwakar;Jamsheera, A.;Zirlianngura, Zirlianngura;Lee, Seung Mok
    • Environmental Engineering Research
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    • v.22 no.2
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    • pp.186-192
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    • 2017
  • The carbon paste electrode (CPE) was modified with the pristine bentonite and hybrid material (HDTMA-modified bentonite). The modified-CPEs are then employed as working electrode in an electrochemical detection of As(V) from aqueous solutions using the cyclic voltammetric measurements. Cyclic voltammograms revealed that As(V) showed reversible behavior onto the working electrode. The hybrid material-modified carbon paste electrode showed significantly enhanced electrochemical signal which was then utilized in the low level detection of As(V). Moreover, the studies were conducted at neutral pH conditions. The electrochemical studies were conducted with scan rates (20 to 200 mV/s) to deduce the mechanism of redox processes involved at the electrode surface. The anodic current was linearly increased, increasing the concentration of As(V) from 5.0 to $35.0{\mu}g/g$ using the hybrid material-modified electrode. This provided fairly a good calibration line for As(V) detection. The presence of varied concentrations of As(III) in the determination of total arsenic was studied. The influence of several cations and anions viz., Cu(II), Mn(II), Zn(II), Pb(II), Cd(II), Fe(III), $Cl^-$, $NO_3{^-}$, $PO_4{^{3-}}$, EDTA and glycine in the detection of As(V) from aqueous solution was also studied. Further, in an attempt to simulate the real matrix analysis, the tap water sample was spiked with As(V) and subjected for As(V) detection using the modified-CPE.

Biomimetic Copper Complex Containing Polymer Modified Electrode for Electrocatalytic Reduction of Oxygen

  • Saravanakumar, D.;Nagarale, Rajaram Krishna;Jirimali, Harish Chandra;Lee, Jong Myung;Song, Jieun;Lee, Junghyun;Shin, Woonsup
    • Journal of Electrochemical Science and Technology
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    • v.7 no.4
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    • pp.298-305
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    • 2016
  • The development of non-precious metal based electrocatalysts is highly desired for the oxygen reduction reaction (ORR) as alternates to noble metal based ORR electrocatalysts. Herein, we report mononulcear copper(II) complex $[CuLbpy]ClO_4$ (L=4-[(2-hydroxyphenylimino)methyl]benzoic acid) containing poly(allylamine.HCl) polymer (PAlACuLbpy) as an electrocatalyst for oxygen reduction reaction (ORR). PAlACuLbpy was mixed with poly(acrylic acid) and tetraethylortho silicate to prepare a composite and then deposited on the screen printed electrode surface. The modified electrode (PAlACuLbpy/PCE) is highly stable and showed a quasi-reversible redox behavior with $E_{1/2}=-0.2V$ vs. Ag/AgCl(3 M KCl) in 0.1 M phosphate buffer at pH 7 under argon atmosphere. PAlACuLbpy/PCE exhibited a remarkable ORR activity with an onset potential of -0.1 V vs Ag/AgCl in 0.1 M PB (pH 7) in the presence of oxygen. The kinetics for ORR was studied by rotating disk voltammetry in neutral aqueous medium and the results indicated that the number of electrons involving in the ORR is four and the conversion products are water and hydrogen peroxide.

Growth and Electrochemical Behavior of Poly[Ni(saldMp)] on Carbon Nanotubes as Potential Supercapacitor Materials

  • Zhang, Yakun;Li, Jianling;Kang, Feiyu;Wang, Xindong;Ye, Feng;Yang, Jun
    • Bulletin of the Korean Chemical Society
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    • v.33 no.6
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    • pp.1972-1978
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    • 2012
  • The polymer of (2,2-dimethyl-1,3-propanediaminebis(salicylideneaminato))-nickel(II), Ni(saldMp), was deposited on multi-walled carbon nanotubes (MWCNTs) substrate by the route of potential linear sweep. The nano structures of poly[Ni(saldMp)] have been obtained by adjusting the monomer concentration of 0.1, 0.2, 0.5, 1.0 and 1.5 mmol $L^{-1}$. The poly[Ni(saldMp)] prepared in acetonitrile solution with monomer concentration of 1.0 mmol $L^{-1}$ shows the fastest growth rate. The effects of potential window on charge-discharge efficiency and electrodeposition scan number on capacitance performance were discussed. Poly[Ni(saldMp)] prepared with less electrodeposition scans exhibits higher capacitance, but this goes against the improvement of the whole electrode capacitance. Sample with 8 deposition scans is the best compromise with the geometric specific capacitance 3.53 times as high as that of pure MWCNTs, and 1.24 times for the gravimetric specific capacitance under the test potential window 0.0-1.0 V.

Preparation and properties of $LiCoO_2$ cathode for Li rechargeable cell (리튬 2차전지용 $LiCoO_2$양극의 제조 및 특성)

  • 문성인;정의덕;도칠훈;윤문수
    • Electrical & Electronic Materials
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    • v.7 no.4
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    • pp.317-324
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    • 1994
  • In this study, new preparation method of LiCoO$_{2}$ was applied to develop cathode active material for Li rechargeable cell, and followed by X-ray diffraction analysis, electrochemical properties and initial charge/discharge characteristics as function of current density. HC8A72- and CC9A24-LiCoO$_{2}$ were prepared by heating treatment of the mixture of LiOH H$_{2}$O/CoCO$_{3}$(1:1 mole ratio) and the mixture of Li$_{2}$CO$_{3}$/CoCO$_{3}$(1:2 mole ratio) at 850 and 900.deg. C, respectively. Two prepared LiCoO$_{2}$s were identified as same structure by X-ray diffraction analysis. a and c lattice constant were 2.816.angs. and 14.046.angs., respectively. The electrochemical potential of CFM-LiCoO$_{2}$(Cyprus Foote Mineral Co.'s product), HC8A72-LiCoO$_{2}$ and CC9A24 LiCoO$_{2}$ electrode were approximately between 3.32V and 3.42V vs. Li/Li reference electrode. Stable cycling behavior was obtained during the cyclic voltammetry of LiCoO$_{2}$ electrode. According as scan rate increases, cathodic capacity decreases, but redox coulombic efficiency was about 100% at potential range between 3.6V and 4.2V vs. Li/Li reference electrode. Cathodic capacity of HC8A72-LiCoO$_{2}$ was 32% higher than that of CFM-LiCoO$_{2}$ and that of CC9A24-LiCoO$_{2}$ was 47% lower than that of CFM-LiCoO$_{2}$ at 130th cycle in the condition of lmV/sec scan rate. Constant cur-rent charge/discharge characteristics of LiCoO$_{2}$/Li cell showed increasing Ah efficiency with initial charge/discharge cycle. Specific discharge capacities of CFM and HC8A72-LiCoO$_{2}$ cathode active materials were about 93mAh/g correspondent to 34% of theretical value, 110mAh/g correspondent to 40% of theretical value, respectively. In the view of reversibility, HC8A72-LiCoO$_{2}$ was also more excellent than CFM- and CC9A24-LiCoO$_{2}$.

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Continuous Wet Oxidation of TCE over Supported Metal Oxide Catalysts (금속산화물 담지촉매상에서 연속 습식 TCE 분해반응)

  • Kim, Moon Hyeon;Choo, Kwang-Ho
    • Korean Chemical Engineering Research
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    • v.43 no.2
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    • pp.206-214
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    • 2005
  • Heterogeneously-catalyzed oxidation of aqueous phase trichloroethylene (TCE) over supported metal oxides has been conducted to establish an approach to eliminate ppm levels of organic compounds in water. A continuous flow reactor system was designed to effect predominant reaction parameters in determining catalytic activity of the catalysts for wet TCE decomposition as a model reaction. 5 wt.% $CoO_x/TiO_2$ catalyst exhibited a transient period in activity vs. on-stream time behavior, suggesting that the surface structure of the $CoO_x$ might be altered with on-stream hours; regardless, it is probable to be the most promising catalyst. Not only could the bare support be inactive for the wet decomposition reaction at $36^{\circ}C$, but no TCE removal also occurred by the process of adsorption on $TiO_2$ surface. The catalytic activity was independent of all particle sizes used, thereby representing no mass transfer limitation in intraparticle diffusion. Very low TCE conversion appeared for $TiO_2$-supported $NiO_x$ and $CrO_x$ catalysts. Wet oxidation performance of supported Cu and Fe catalysts, obtained through an incipient wetness and ion exchange technique, was dependent primarily on the kinds of the metal oxides, in addition to the acidic solid supports and the preparation routes. 5 wt.% $FeO_x/TiO_2$ catalyst gave no activity in the oxidation reaction at $36^{\circ}C$, while 1.2 wt.% Fe-MFI was active for the wet decomposition depending on time on-stream. The noticeable difference in activity of the both catalysts suggests that the Fe oxidation states involved to catalytic redox cycle during the course of reaction play a significant role in catalyzing the wet decomposition as well as in maintaining the time on-stream activity. Based on the results of different $CoO_x$ loadings and reaction temperatures for the decomposition reaction at $36^{\circ}C$ with $CoO_x/TiO_2$, the catalyst possessed an optimal $CoO_x$ amount at which higher reaction temperatures facilitated the catalytic TCE conversion. Small amounts of the active ingredient could be dissolved by acidic leaching but such a process gave no appreciable activity loss of the $CoO_x$ catalyst.

Biogeochemical Effects of Hydrogen Gas on the Behaviors of Adsorption and Precipitation of Groundwater-Dissolved Uranium (지하수 용존 우라늄의 수착 및 침전 거동에서 수소 가스의 생지화학적 영향)

  • Lee, Seung Yeop;Lee, Jae Kwang;Seo, Hyo-Jin;Baik, Min Hoon
    • Economic and Environmental Geology
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    • v.51 no.2
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    • pp.77-85
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    • 2018
  • There would be a possibility of uranium contamination around the nuclear power plants and the underground waste disposal sites, where the uranium could further migrate and diffuse to some distant places by groundwater. It is necessary to understand the biogeochemical behaviors of uranium in underground environments to effectively control the migration and diffusion of uranium. In general, various kinds of microbes are living in soils and geological media where the activity of microbes may be closely connected with the redox reaction of nuclides resulting in the changes of their solubility. We investigated the adsorption and precipitation behaviors of dissolved uranium on some solid materials using hydrogen gas as an electron donor instead of organic matters. Although the effect of hydrogen gas did not appear in a batch experiment that used granite as a solid material, there occurred a reduction of uranium concentration by 5~8% due to hydrogen in an experiment using bentonite. This result indicates that some indigenous bacteria in the bentonite that have utilized hydrogen as the electron donor affected the behavior (reduction) of uranium. In addition, the bentonite bacteria have showed their strong tolerance against a given high temperature and radioactivity of a specific waste environment, suggesting that the nuclear-biogeochemical reaction may be one of main mechanisms if the natural bentonite is used as a buffer material for the disposal site in the future.

Analysis and Mechanistic Investigation of Redox Process of 2-Amino-1-cyclopentene-1-dithiocarboxylate by Adsorptive Stripping Voltammetry on Glassy Carbon Electrode (Glassy Carbon 전극에서의 벗김 전압-전류법을 이용한 2-Amino-1-cyclopentene-1-dithiocarboxylate 의 분석과 전극 반응 메카니즘의 연구)

  • Yoon-Bo Shim;Duk-Soo Park;Sung-Nak Choi;Mi-Sook Won
    • Journal of the Korean Chemical Society
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    • v.32 no.1
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    • pp.37-47
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    • 1988
  • The electrochemical behavior of 2-Amino-1-cyclopentene-1-dithiocarboxylate (acdc) was investigated by the use of polarography, cyclic voltammetry and cathodic stripping voltammetry at glassy carbon electrode. In this study, it was found that the dimer of the acdc was deposited on the glassy carbon electrode via one-electron oxidation process at +0.25V vs. SCE. The ring formation between two dithio group occurs along with the elimination of one sulfur atom. The elimination of sulfur atom occurs via two electron oxidation process at +0.8V vs. SCE. The most sensitive cathodic stripping peak due to the formation of the dimer was observed at -0.85V vs. SCE. The peak relationship between current and concentration was fairly linear in the range of 3${\times}10^{-5}{\sim}1.0{\times}10^{-6}$M. The preconcentration procedure enhanced the sensitivity about 100 times for the analysis of acdc using diffusion current. Detection limit was found to be $2.5{\times}10^{-7}$M and relative standard deviation was ${\pm}$4.1 % at $5.0{\times}10^{-6}$M DC polarography.

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Growth and Structural Properties of Fe Thin Films Electrodeposited on n-Si(111) (n-Si(111) 기판 위에 전기증착에 의한 Fe 박막의 성장과 구조적 특성)

  • Kim Hyun-Deok;Park Kyeong-Won;Lee Jong-Duk
    • Journal of the Korea Institute of Information and Communication Engineering
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    • v.10 no.9
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    • pp.1663-1670
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    • 2006
  • Single crystal Fe thin films were grown directly onto n-Si(111) substrates by pulsed electrodeposition. Cyclic Voltammogram(CV) indicated that the $Fe^{2+}/n-Si(111)$ interface shows a good diode behavior by forming a Schottky barrier. From Mott-Schottky (MS) relation, it is found that the flat-band potential of n-Si(111) substrate and equilibrium redox potential of $Fet^{2+}$ ions are -0.526V and -0.316V, respectively. The nucleation and growth kinetics at the initial reaction stages of Fe/n-Si(111) substraste was studied by current transients. Current transients measurements have indicated that the deposition process starts via instantaneous nucleation and 3D diffusion limited growth. After the more deposition, the deposition flux of Fe ions was saturated with increase of deposition time. from the as-deposited sample obtained using the potential pulse of 1.4V and 300Hz, it is found that Fe nuclei grows to three dimensional(3D) islands with the average size of about 100nm in early deposition stages. As the deposition time increases, the sizes of Fe nuclei increases progressively and by a coalescence of the nuclei, a continuous Fe films grow on the Si surface. In this case, the Fe films show a highly oriented columnar structure and x-ray diffraction patterns reveal that the phase ${\alpha}-Fe$ grows on the n-Si(111) substrates.

Stability Characteristics of Sn Species Behavior on Surface of a Sn-modified Pt Electrode for Electrolytic Reduction of Nitrate Ion (질산염 이온의 전해 환원을 위한 Sn-modified Pt 전극 표면에서의 Sn 안정성 거동 특성)

  • Kim, Kwang-Wook;Kim, Seong-Min;Kim, Yeon-Hwa;Lee, Eil-Hee;Jee, Kwang-Yong
    • Korean Chemical Engineering Research
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    • v.45 no.5
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    • pp.433-441
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    • 2007
  • This work investigated the stability of a Sn-modified Pt electrode, which was used for reduction of nitrate, fabricated by an adsorption or electro-deposition of Sn on Pt. In order to find the causes for instability of the electrode, the effects of the solutions in which the electrode was used and the potential applied to the electrode on the electrochemical and metallurgical behaviors of Sn on Pt were studied. The Sn of freshly- prepared modified-Sn Pt electrode existed as Sn hydroxide form, which brought about an easy loss of the electro-activity of the electrode even staying in water, especially in acid solution. When the Sn-modified Pt electrode was used for the reduction of nitrate, the electro-activity of the electrode was affected depending on the potential applied to the electrode. When a more negative potential than the redox equilibrium potential between $Sn(OH)_2$ and Sn was applied to the electrode, the Sn hydroxide was converted to Sn that could diffused into Pt, which leaded to the loss of electro-activity of the electrode as well. The solid diffusion of Sn increased linearly with the applied potential. The Sn-electrodeposited Pt electrode which had more Sn on the electrode was more favorable to maintaining the integrity of the electrode during the reduction of nitrate than the Sn-adsorbed Pt electrode prepared in the under-potential deposition way.