• Title/Summary/Keyword: Electrochemical Oxidation

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Tri-branched tri-anchoring organic dye for Visible light-responsive dye-sensitized photoelectrochemical water-splitting cells (염료감응형 광전기화학 물분해 전지용 Tri-branched tri-anchoring organic dye 개발)

  • Park, Jeong-Hyun;Kim, Jae-Hong;Ahn, Kwang-Soon
    • 한국신재생에너지학회:학술대회논문집
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    • 2010.06a
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    • pp.87-87
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    • 2010
  • Photoelectrochemical (PEC) systems are promising methods of producing H2 gas using solar energy in an aqueous solution. The photoelectrochemical properties of numerous metal oxides have been studied. Among them, the PEC systems based on TiO2 have been extensively studied. However, the drawback of a PEC system with TiO2 is that only ultraviolet (UV) light can be absorbed because of its large band gap (3.2 - 3.4 eV). Two approaches have been introduced in order to use PEC cells in the visible light region. The first method includes doping impurities, such as nitrogen, into TiO2, and this technique has been extensively studied in an attempt to narrow the band gap. In comparison, research on the second method, which includes visible light water splitting in molecular photosystems, has been slow. Mallouk et al. recently developed electrochemical water-splitting cells using the Ru(II) complex as the visible light photosensitizer. the dye-sensitized PEC cell consisted of a dye-sensitized TiO2 layer, a Pt counter electrode, and an aqueous solution between them. Under a visible light (< 3 eV) illumination, only the dye molecule absorbed the light and became excited because TiO2 had the wide band gap. The light absorption of the dye was followed by the transfer of an electron from the excited state (S*) of the dye to the conduction band (CB) of TiO2 and its subsequent transfer to the transparent conducting oxide (TCO). The electrons moved through the wire to the Pt, where the water reduction (or H2 evolution) occurred. The oxidized dye molecules caused the water oxidation because their HOMO level was below the H2O/O2 level. Organic dyes have been developed as metal-free alternatives to the Ru(II) complexes because of their tunable optical and electronic properties and low-cost manufacturing. Recently, organic dye molecules containing multi-branched, multi-anchoring groups have received a great deal of interest. In this work, tri-branched tri-anchoring organic dyes (Dye 2) were designed and applied to visible light water-splitting cells based on dye-sensitized TiO2 electrodes. Dye 2 had a molecular structure containing one donor (D) and three acceptor (A) groups, and each ended with an anchoring functionality. In comparison, mono-anchoring dyes (Dye 1) were also synthesized. The PEC response of the Dye 2-sensitized TiO2 film was much better than the Dye 1-sensitized or unsensitized TiO2 films.

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Theoretical and quantitative structural relationships of the electrochemical properties of Cis-unsaturated thiocrown ethers and n-type material bulk-heterojunction polymer solar cells as supramolecular complexes [X-UT-Y]@R (R = PCBM, p-EHO-PCBM, and p-EHO-PCBA)

  • Taherpour, Avat Arman;Biuki, Farzaneh
    • Journal of Information Display
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    • v.12 no.3
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    • pp.145-152
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    • 2011
  • Since the discovery of fullerenes as a class of nanostructure compounds, many potential applications have been suggested for their unusual structures and properties. The isolated pentagon rule (IPR) states that all pentagonal carbon rings are isolated in the most stable fullerene. Fullerenes $C_n$ are a class of spherical carbon allotrope group with unique properties. Electron transfer between fullerenes and other molecules is thought to involve the transfer of electrons between the molecules surrounding the fullerene cage. One class of electron transfer molecules is the methanofullerene derivatives ([6,6]-phenyl $C_{61}$-butyric acid methyl ester (PCBM), 4-(2-ethylhexyloxy)-[6,6]-phenyl $C_{61}$-butyric acid methyl ester (p-EHO-PCBM), and 4-(2-ethylhexyloxy)-[6,6]-phenyl $C_{61}$-butyric acid (p-EHO-PCBA), 10-12). It has been determined that $C_{60}$ does not obey IPR. Supramolecular complexes 1-9 and 10-12 are shown to possess a previously unreported host.guest interaction for electron transfer processes. The unsaturated, cis-geometry, thiocrown ethers, (1-9) (described as [X-UT-Y], where X and Y indicate the numbers of carbon and sulfur atoms, respectively), are a group of crown ethers that display interesting physiochemical properties in the light of their conformational restriction compared with a corresponding saturated system, as well as the sizes of their cavities. Topological indices have been successfully used to construct mathematical methods that relate structural data to various chemical and physical properties. To establish a good relationship between the structures of 1-9 with 10-12, a new index is introduced, ${\mu}_{cs}$. This index is the ratio of the sum of the number of carbon atoms ($n_c$) and the number of sulfur atoms ($n_s$) to the product of these two numbers for 1-9. In this study, the relationships between this index and oxidation potential ($^{ox}E_1$) of 1-9, as well as the first to third free energies of electron transfer (${\Delta}G_{et(n)}$, for n = 1-3, which is given by the Rehm-Weller equation) between 1-9 and PCBM, p-EHO-PCBM, and p-EHO-PCBA (10-12) as [X-UT-Y]@R(where R is the adduct PCBM, p-EHO-PCBM, and p-EHO-PCBA group) (13-15) supramolecular complexes are presented and investigated.

Identification of Internal Resistance of Microbial Fuel Cell by Electrochemical Technique and Its Effect on Voltage Change and Organic Matter Reduction Associated with Power Management System (전기화학적 기법에 의한 미생물연료전지 내부저항 특성 파악 및 전력관리시스템 연계 전압 변화와 유기물 저감에 미치는 영향)

  • Jang, Jae Kyung;Park, Hyemin;Kim, Taeyoung;Yang, Yoonseok;Yeo, Jeongjin;Kang, Sukwon;Paek, Yee;Kwon, Jin Kyung
    • Journal of Biomedical Engineering Research
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    • v.39 no.5
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    • pp.220-228
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    • 2018
  • The internal resistance of microbial fuel cell (MFC) using stainless steel skein for oxidizing electrode was investigated and the factors affecting the voltage generation were identified. We also investigated the effect of power management system (PMS) on the usability for MFC and the removal efficiency of organic pollutants. The performance of a stack microbial fuel cell connected with (PMS) or PMS+LED was analyzed by the voltage generation and organic matter reduction. The maximum power density of the unit cells was found to be $5.82W/m^3$ at $200{\Omega}$. The maximum current density was $47.53A/m^3$ without power overshoot even under $1{\Omega}$. The ohmic resistance ($R_s$) and the charge transfer resistance ($R_{ct}$) of the oxidation electrode using stainless steel skein electrode, were $0.56{\Omega}$ and $0.02{\Omega}$, respectively. However, the sum of internal resistance for reduction electrode using graphite felts loaded Pt/C catalyst was $6.64{\Omega}$. Also, in order to understand the internal resistance, the current interruption method was used by changing the external resistance as $50{\Omega}$, $300{\Omega}$, $5k{\Omega}$. It has been shown that the ohm resistance ($R_s$) decreased with the external resistance. In the case of a series-connected microbial fuel cell, the reversal phenomenon occurred even though two cells having the similar performance. However, the output of the PMS constantly remained for 20 hours even when voltage reversal occurred. Also the removal ability of organic pollutants (SCOD) was not reduced. As a result of this study, it was found that buffering effect for a certain period of time when the voltage reversal occurred during the operation of the microbial fuel cell did not have a serious effect on the energy loss or the operation of the microbial fuel cell.

Structural and electrochemical characterization of K2NiF4 type layered perovskite as cathode for SOFCs (K2NiF4 type 층상 페롭스카이트 구조 La(Ca)2Ni(Cu)O4-δ의 SOFC 양극 특성 및 결정구조 평가)

  • Myung, Jae-ha;Hong, Youn-Woo;Lee, Mi Jai;Jeon, Dae-Woo;Lee, Young-Jin;Hwang, Jonghee;Shin, Tae Ho;Paik, Jong Hoo
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.25 no.3
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    • pp.116-120
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    • 2015
  • $La_2NiO_{4+{\delta}}$ based oxides, a mixed electronic-ionic conductors (MIECs) with $K_2NiF_4$ type structure, have been considerably investigated in recent decades as electrode materials for advanced solid oxide fuel cells (SOFCs) due to their high electrical conductivity, and oxidation reduction reaction (ORR). In this study, structure properties of $La(Ca)_2Ni(Cu)O_{4+{\delta}}$ were studied as a potential cathode for intermediate temperature SOFCs (IT-SOFCs).

TiO2 Nanotubular Formation on Grade II Pure Titanium by Short Anodization Processing (Grade II 순수 타이타늄의 단시간 양극산화에 의한 TiO2 나노튜브 형성)

  • Lee, Kwangmin;Kim, Yongjae;Kang, Kyungho;Yoon, Duhyeon;Rho, Sanghyun;Kang, Seokil;Yoo, Daeheung;Lim, Hyunpil;Yun, Kwiduk;Park, Sangwon;Kim, Hyun Seung
    • Korean Journal of Materials Research
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    • v.23 no.4
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    • pp.240-245
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    • 2013
  • Electrochemical surface treatment is commonly used to form a thin, rough, and porous oxidation layer on the surface of titanium. The purpose of this study was to investigate the formation of nanotubular titanium oxide arrays during short anodization processing. The specimen used in this study was 99.9% pure cp-Ti (ASTM Grade II) in the form of a disc with diameter of 15 mm and a thickness of 1 mm. A DC power supplier was used with the anodizing apparatus, and the titanium specimen and the platinum plate ($3mm{\times}4mm{\times}0.1mm$) were connected to an anode and cathode, respectively. The progressive formation of $TiO_2$ nanotubes was observed with FE-SEM (Field Emission Scanning Electron Microscopy). Highly ordered $TiO_2$ nanotubes were formed at a potential of 20 V in a solution of 1M $H_3PO_4$ + 1.5 wt.% HF for 10 minutes, corresponding with steady state processing. The diameters and the closed ends of $TiO_2$ nanotubes measured at a value of 50 cumulative percent were 100 nm and 120 nm, respectively. The $TiO_2$ nanotubes had lengths of 500 nm. As the anodization processing reached 10 minutes, the frequency distribution for the diameters and the closed ends of the $TiO_2$ nanotubes was gradually reduced. Short anodization processing for $TiO_2$ nanotubes of within 10 minutes was established.

Decrease of PEMFC Performance by Toluene in Air (공기 중 톨루엔에 의한 고분자전해질연료전지의 성능감소)

  • Lee, Ho;Song, Jin-Hoon;Kim, Ki-Joong;Kim, Sae-Hoon;Ahn, Byung-Ki;Lim, Tae-Won;Park, Kwon-Pil
    • Korean Chemical Engineering Research
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    • v.49 no.1
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    • pp.15-20
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    • 2011
  • The contamination effect of toluene in the airstream on PEM fuel cell performance was studied with various toluene concentration under different operation conditions. And the recovery of the cell performance by applying clean air and the removal of toluene in the air by adsorption of active carbon were investigated. The toluene concentration range used in the experiments was from 0.1 ppm to 5.0 ppm. The performance degradation and recovery were measured by constant-current discharging and electrochemical impedance spectroscopy(EIS). Toluene adsorption capacity of KOH impregnated active carbon was obtained from the adsorption isotherm curve. The severity of the contamination increased with increasing toluene concentration, current density and air stoichiometry, but decrease with increasing relative humidity. The cell performance was recovered by toluene oxidation with oxygen and water in humidified neat air. EIS showed that the increase of charge transfer resistance due to toluene adsorption on Pt surface mainly reduced the performance of PEMFC. Toluene adsorption capacity of active carbon decreased as KOH weight increased in KOH impregnated active carbon.

Study on Oxidation or Reduction Behavior of Cs-Te-O System with Gas Conditions of Voloxidation Process (휘발산화 공정 조건에 따른 Cs-Te-O 시스템의 산화 환원 거동 연구)

  • Park, Byung Heung
    • Korean Chemical Engineering Research
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    • v.51 no.6
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    • pp.700-708
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    • 2013
  • Pyroprocessing has been developed for the purpose of resolving the current spent nuclear fuel management issue and enhancing the recycle of valuable resources. Pyroprocessing has been developed with the dry technologies which are performed under high temperature conditions excluding any aqueous processes. Pyro-processes which are based on the electrochemical principles require pretreatment processes and a voloxidation process is considered as a pretreatment step for an electrolytic reduction process. Various kinds of gas conditions are applicable to the voloxidation process and the understanding of Cs behavior during the process is of importance for the analyses of waste characteristics and heat load on the overall pyroprocessing. In this study, the changes of chemical compounds with the gas conditions were calculated by analyzing gas-solid reaction behavior based on the chemical equilibria on a Cs-Te-O system. $Cs_2TeO_3$ and $Cs_2TeO_4$ were selected after a Tpp diagram analysis and it was confirmed that they are relatively stable under oxidizing atmospheres while it was shown that Cs and Te would be removed by volatilization under reducing atmosphere at a high temperature. This work provided basic data for predicting Cs behavior during the voloxidation process at which compounds are chemically distributed as the first stage in the pyroprocessing and it is expected that the results would be used for setting up material balances and related purposes.

Lithium Battery Anode Properties of Ball-Milled Graphite-Silicon Composites (볼밀링법으로 제조된 흑연-실리콘 복합체의 리튬전지 음전극 특성)

  • Kang, Kun-Young;Shin, Dong Ok;Lee, Young-Gi;Kim, Kwang Man
    • Korean Chemical Engineering Research
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    • v.51 no.4
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    • pp.411-417
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    • 2013
  • To use as an anode material of lithium secondary battery, graphite-silicon composite powders are prepared by ball-milling with silicon nanoparticles (average diameter 100 nm, 0~50 wt%) and graphite powder (average diameter $15{\mu}m$) and their electrochemical properties are examined. As the silicon content increases, the graphite becomes smaller by the ball-milling and amorphous phase appears whereas the silicon do not suffer the change of nanocrystalline phases and embeds within the amorphous phase of graphite. Cyclic voltammetry at low scan rate reveals that typical oxidation peaks of graphite and silicon appear at 0.2~0.35 and 0.55~0.6 V, respectively, with higher reversibility for repeated cycles. In contrast, the high-scan-rate redox behavior is very irreversible for repeated cycles. High irreversible capacity is exhibited in the initial charging-discharging cycles, but it diminishes as the cycle number increases. The saturated discharge capacity achieves about 485 mAh $g^{-1}$ at 50th cycle for the composite of Si 20 wt%. This is due to the formation of amorphous graphite morphology by the adequate composition (C:Si=8:2 w/w), which efficiently buffers the volume change during alloying/dealloying between silicon and lithium.

Electrochemical Properties of Pyrrole/Thiophene Polymer Composite (피롤/티오펜 고분자 복합체의 전기화학적 성질)

  • Cha, Seong Keuck;Choi, Kyu Seong;Ahn, Byuong Kee;Kang, Sang Jin
    • Journal of the Korean Chemical Society
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    • v.40 no.7
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    • pp.467-473
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    • 1996
  • Although a polypyrrole shows better electrical conductivity, 100∼400 ${\Omega}^{-1}cm^{-1}$, than other organic conducting polymers, its electrical conductivity will be worsen in the presence of the oxygen due to its easy oxidation. On the other hand, polythiophene shows better stability in the air while its electrcal conductivity is poor compared to the polypyrrole. We succeed to develope the mixed polymer electrode that is stable in the air and shows a good redox characteristics. The mixed polymer electrode has been prepared by the electrical polymerization of polypyrrole on the Pt electrode as 1.70 C$cm^{-2}$ and then coating with polythiophene as 0.34 C$cm^{-2}$. The polymerization rate of polythiophene was $3.89{\times}10^{-8}$ at the bare Pt electrode and $6.07{\times}10^{-8}cms^{-1}$ at the mixed polymer electrode. And the standard rate constants of each electrode were $5.16{\times}10^{-6}\;and\;3.94{\times}10^{-4} cms^{-1}$ respectively. Also, the electrocatalytic rate of the polypyrrole polymer electrode was $3.45{\times}10^{-3}cm^3mol^{-1}s^{-1}.$ We found the immobilized layer at the modified electrode acted as an electrocatalyst. Finally, this polymerization process at the Pt electrode was the electron transfer controlled, but that the mixed polymer electrode was the diffusion and charge transfer controlled.

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EFFECTS OF DIFFERENT OXIDIZED SURFACES OF IMPLANT ON OSSEOINTEGRATION; RESONANCE FREQUENCY AND HISTOMORPHOMETRIC ANALYSIS STUDY IN MINI-PIGS (다양한 양극산화막 처리방법이 임플란트 골유착에 미치는 영향)

  • Kwon, Kyung-Hwan;Min, Seung-Ki;Sung, Dae-Hyuk;Choi, Jae-Young;Choi, Seung-Lim;Cha, Su-Ryeon;Oh, Hee-Kyun
    • Maxillofacial Plastic and Reconstructive Surgery
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    • v.29 no.5
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    • pp.383-393
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    • 2007
  • The aim of the present study is to investigate the effect of anodized surface of osseointegration implants by using of resonance frequency analysis (RFA) and histomorphometric analysis. A total of 96 screw-shaped implants were devided into 4 groups. Seventy-two implants were prepared by electrochemical oxidation with 3 different ways; Group 1 (n=24) were prepared at galvanostatic mode in 0.25M sulfuric acid and phosphoric acid, Group 2 (n=24) were prepared at galvanostatic mode in calcium glycerophosphate and calcium acetate, and Group 3 (n=24) were prepared at galvanostatic mode in 0.25M sulfuric acid and phosphoric acid followed by Calcium metaphosphate(CMP) coating. Control group (n=24) were the RBM surfaced implants. The implants were placed in the mandibles of 12 mini pigs. Bone tissue responses were evaluated by resonance frequency analysis(RFA) and histomorphometric analysis that were undertaken at 2, 4 and 6weeks after implant placement. The following result were obtained. 1. Twenty-two of 96 implants (4 in control group, 5 in group 1, 7 in group 2, and 6 in group 3) were failed due to faliure of osseoitegration. The failure rate of osseointegration was 22.9%. 2. The mean values of RFA in control, group 2 and groups 3 showed the similar values, but there was no significant difference among groups. 3. Histomorphometric evaluation demonstrated significantly higher bone-to-implant contact ratio in group 2 at 3 and 4 weeks after implant placement than other groups (p<0.05), but there was no significant difference among groups at 6weeks after implant placement.