• Title/Summary/Keyword: Redox stability

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A Basic Study on Non-aqueous Electrolysis of Neodymium for Room-temperature Metallurgy (상온제련을 위한 네오디뮴의 비수계 전해 기초연구)

  • Park, Jesik;Lee, Churl Kyoung
    • Resources Recycling
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    • v.27 no.4
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    • pp.29-35
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    • 2018
  • In this study, the electrochemical redox behavior of neodymium in non-aqueous electrolytes was investigated to confirm the possibility of neodymium metallurgy at room temperature. The non-aqueous electrolytes include ionic liquids such as $[C_4mim]PF_6$, $[C_4mim]Cl$, and $[P_{66614}]PF_6$, ethanol which are highly soluble in neodymium salts, and mixed electrolytes based on carbonate with highly electrochemical stability. The electrochemical redox properties of neodymium were better than those of other electrolytes in the case of the mixed electrolyte based on ethylene carbonate (EC)/di-ethylene carbonate (DEC). Ethanol was added to improve the physical properties of the mixed electrolyte. Thorough the analysis about ionic conductivity of EC/DEC ratio, ethanol content and $NdCl_3$ concentration, the best electrolyte composition was 50 vol% content of ethanol and 0.5 M of $NdCl_3$. Using cyclic voltametry and linear sweep voltametry, a current peak estimated at -3.8 V (vs. Pt-QRE) was observed as a limiting current of neodymium reduction. Potentiostatic electrolysis for 18 hours at room temperature at -6 V (vs. Pt-QRE) confirmed that metallic neodymium was electrodeposited.

Photocurrent and Its Stability Enhancement of Dye-sensitized Nanoparticle $TiO_2$ Solar Cells (염료감응 나노입자 $TiO_2$ 태양전지의 광전류와 그 안정성 향상)

  • Chae Won-Weok;Kang Tae-Sik;Kim Kang-Jin
    • Journal of the Korean Electrochemical Society
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    • v.2 no.4
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    • pp.232-236
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    • 1999
  • A solar cell based on dye-sensitized photoelectric conversion was studied by electrochemical and spec-trofluorometric methods for the purposes of enhancing its efficiency and stability of $TiO_2$ solar cells. Nanocrystalline $TiO_2$ was used to prepare photoelectrodes, and photosensitizing dyes such as malachite green oxalate, basic blue3, rhodamine B, and bromocresol purple were chosen as sensitizers. Electrochemical oxidation potentials and absorption and emission wavelengths of dyes were used to determine energy levels of the dyes. By comparing excited energy levels of the dyes with the conduction band edge potential $(E_{c,s})\;of\;TiO_2$ calculated by using the flat-band potential $(E_{fb})\;of\;TiO_2$, properties of a dye required to fabricate a high efficient photosensitizing solar cell with high short-circuit current $(J_{sc})$ were suggested. Enhanced stability of photocurrent was obtained by coating a $TiO_2|ITO$ electrode with Polypyrrole that Possibly Prevented the recombination between the conduction band electrons and oxidized dyes and suppressed the direct electrode redox reactions of dyes on ITO.

Morphology-dependent Nanocatalysis: Rod-shaped Oxides

  • Shen, Wenjie
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.130-131
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    • 2013
  • Nanostructured oxides are widely used in heterogeneous catalysis where their catalytic properties are closely associated with the size and morphology at nanometer level. The effect of particle size has been well decumented in the past two decades, but the shape of the nanoparticles has rarely been concerned. Here we illustrate that the redox and acidic-basic properties of oxides are largely dependent on their shapes by taking $Co_3O_4$, $Fe_2O_3$, $CeO_2$ and $La_2O_3$ nanorods as typical examples. The catalytic activities of these rod-shaped oxides are mainly governed by the nature of the exposed crystal planes. For instance, the predominant presence of {110} planes which are rich in active $Co^{3+}$ on $Co_3O_4$ nanorods led to a much higher activity for CO oxidation than the nanoparticles that mainly exposed the {111} planes. The simultaneous exposure of iron and oxygen ions on the surface of $Fe_2O_3$ nanorods have significantly enhanced the adsorption and activation of NO and thereby promoted the efficiency of DeNOx process. Moreover, the exposed surface planes of these rod-shaped oxides mediated the reaction performance of the integrated metal-oxide catalysts. Au/$CeO_2$ catalysts exhibited outstanding stability under water-gas shift conditions owing to the strong bonding of gold particle on the $CeO_2$ nanorods where the formed gold-ceria interface was resistant towards sintering. Cu nanoparticles dispersed on $La_2O_3$ nanorods efficiently catalyzed transfer dehydrogenation of primary aliphatic alcohols based on the uniue role of the exposed {110} planes on the support. Morphology control at nanometer level allows preferential exposure of the catalytically active sites, providing a new stragegy for the design of highly efficient nanostructured catalysts.

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Effect of Fabrication Method of Anode on Performance in Enzyme Fuel Cells (효소연료전지의 Anode 제조조건이 성능에 미치는 영향)

  • Lee, Se-Hoon;Hwang, Byung-Chan;Lee, Hye-Ri;Kim, Young-Sook;Chu, Cheun-Ho;Na, Il-Chai;Park, Kwon-Pil
    • Korean Chemical Engineering Research
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    • v.53 no.6
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    • pp.667-671
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    • 2015
  • Enzyme fuel cells were operated with cells composed of enzyme anode and PEMFC cathode. Enzyme anodes was fabricated by compression of a mixture of graphite particle, glucose oxidase(Gox) as a enzyme and ferrocene as a redox mediator, and then coated with Nafion ionomer solution. Performances of enzyme unit cell were measured with variation of anode manufacture factors, to find optimum condition of enzyme anode. Optimum pressure was 8.89MPa for enzyme anode pressing process. Highest power density was obtained at 60% graphite composition in enzyme anode. Optimum glucose concentration was 1.7 mol/l in anode substrate solution. The enzyme anode was stabilized by two times of deeping in Nafion solution for 1 sec.

Preparation of Solid Polymer Electrolytes of PSf-co-PPSS/Heterooolyacid [HPA] Composite Membrane for Hydrogen Production via Water Elecrolysis (PSf-co-PPSS/HPA를 이용한 수소제조 수전해용 고체 고분자 전해질 복합 막의 제조)

  • Jung, Yun-Kyo;Lee, Hyuck-Jae;Jang, In-Young;Hwang, Gab-Jin;Bae, Ki-Kwang;Sim, Kyu-Sung;Kang, An-Soo
    • Transactions of the Korean hydrogen and new energy society
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    • v.16 no.2
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    • pp.103-110
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    • 2005
  • Proton conducting solid polymer electrolyte (SPE) membranes have been used in many energy technological applications such as water electolysis, fuel cells, redox-flow battery, and other electrochemical devices. The availability of stable membranes with good electrochemical characteristics as proton conductivity at high temperatures above 80 $^{\circ}C$ and low cost are very important for its applications. However, the presently available perfluorinated ionomers are not applicable because of high manufacturing cost and high temperature use to the decrease in the proton conductivity and mechanical strength. In order to make up for the weak points, the block copolymer (BPSf) of polysulfone and poly (phenylene sulfide sulfone) were synthesized and sulfonated. The electrolyte membranes were prepared with phosphotungstic acid (HPA)/sulfonated BPSf via solution blending. This study would be desirable to investigate the interaction between the HPA and sulfonated polysulfone. The results showed that the characteristics of SPSf/HPA blend membrane was a better than Nafion at high temperature, 100 $^{\circ}C$. These membranes proved to have a high proton conductivity, $6.29{\times}10-2$ S/cm, a water content, 23.9%, and a ion exchange capacity, 1.97 meq./g dry membrane. Moreover, some of the membranes kept their high thermal and mechanical stability.

Preferential CO Oxidation over Ce-Promoted Pt/γ-Al2O3 Catalyst (Ce가 첨가된 Pt/γ-Al2O3 촉매의 선택적 CO 산화반응 특성)

  • Kim, Kihyeok;Koo, Keeyoung;Jung, Unho;Yoon, Wanglai
    • Transactions of the Korean hydrogen and new energy society
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    • v.23 no.6
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    • pp.640-646
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    • 2012
  • The effect of Ce promotion over 1wt% $Pt/{\gamma}-Al_2O_3$ catalysts on the CO conversion and $CO_2$ selectivity was investigated in preferential CO oxidation (PrOx) to reduce the CO concentration less than 10 ppm in excess $H_2$ stream for polymer electrolyte membrane fuel cell (PEMFC). Ce-promoted 1wt% $Pt/{\gamma}-Al_2O_3$ catalysts were prepared by incipient wetness impregnation method and the loading amount of Pt was fixed at 1wt%. The content of Ce promoter which has excellent oxygen storage and transfer capability due to the redox property was adjusted from 0 to 1.5wt%. Ce-promoted 1wt% $Pt/{\gamma}-Al_2O_3$ catalysts exhibit high CO conversion and $CO_2$ selectivity at low temperatures below $150^{\circ}C$ due to the improvement of reducibility of surface PtOx species compared with the 1wt% $Pt/{\gamma}-Al_2O_3$ catalyst without Ce addition. When Ce content was more than 1wt%, the catalytic activity was decreased at over $160^{\circ}C$ in PrOx because of competitive $H_2$ oxidation. As a result, 0.5wt% Ce is optimal content not only to achieve high catalytic activity and good stability at low temperatures below $150^{\circ}C$ in the presence of $CO_2$ and $H_2O$ but also to minimize the $H_2$ oxidation at high temperatures.

Stepwise Production of Syngas and Hydrogen from Methane on Ferrite Based Media Added with YSZ (YSZ 첨가 페라이트 매체상에서 메탄으로부터 합성 가스 및 수소의 단계적 생산)

  • Je, Han-Sol;Cha, Kwang-Seo;Kim, Hong-Soon;Lee, Young-Seak;Park, Chu-Sik;Kim, Young-Ho
    • Transactions of the Korean hydrogen and new energy society
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    • v.21 no.1
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    • pp.50-57
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    • 2010
  • Stepwise production of syn-gas and hydrogen from methane on ferrite based media added with yttria-stabilized zirconia (YSZ) was carried out using a fixed bed infrared reactor. In this study, all M-ferrite (M=Co, Cu, Mn and Ni) media were prepared by co-precipitation method, and there the YSZ was added as a binder to improve thermal stability, reactivity, and resistance against carbon deposition. Most of the ferrite media containing YSZ showed the good redox property for temperature programmed reduction/oxidation (TPR/O) tests. Notably, the Cu-substituted ferrite medium with YSZ showed the great resistance against carbon deposition as well as the good reactivity for the stepwise production of syngas and hydrogen. Furthermore, it also showed the good durability without significant deactivation during five repeated cyclic tests.

Change in the photocatalytic activity of ZnO nanoparticles by additive H2O

  • Nam, Sang-Hun;Kim, Myoung-Hwa;Lee, Sang-Duck;Choi, Jin-Woo;Kim, Min-Hee;Boo, Jin-Hyo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.08a
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    • pp.285-285
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    • 2010
  • Zinc oxide (ZnO) is a direct band gap semiconductor with 3.37 eV, which has in a hexagonal wurtzite structure. ZnO is a good candidate for a photocatalyst because it has physical and chemical stability, high oxidative properties, and absorbs of ultraviolet light. During ZnO is irradiated by UV light, redox (reduction and oxidation) reactions will occur on the ZnO surface, generating the radicals O2- and OH. These two powerful oxidizing agents have been proven to be effective in decomposition of harmful organic materials, converting them into CO2 and H2O. Therefore, we assume that oxygen on the surface of ZnO is a very important factor in the photocatalytic activities of ZnO nanoparticles. Recently, ZnO nanoparticles are studied in various application fields by many researchers. Photocatalyst research is progressing much in various application fields. But the ZnO nanoparticles have disadvantage that is unstable in water in comparison titanium dioxide (TiO2). The Zn(OH)2 was formed at the ZnO surface and ZnO become inactive as a photocatalyst when ZnO is present in the solution. Therefore, we prepared synthesized ZnO nanoaprticles that were immersed in the water and dried in the oven. After that, we measured photocatalytic activities of prepared samples and find the cause of their phtocatalytic activity changes. The characterization of ZnO nanoparticles were analyzed by Scanning Electron Microscopy (SEM), X-ray diffraction (XRD) and BET test. Also we defined the photocatalytic activity of ZnO nanoparticles using UV-VIS Spectroscopy. And we explained changing of photocatalytic activity after the water treatment using X-ray Photoelectron Spectroscopy (XPS).

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Thermodynamic Control in Competitive Anchoring of N719 Sensitizer on Nanocrystalline $TiO_2$ for Improving Photoinduced Electrons

  • Lim, Jong-Chul;Kwon, Young-Soo;Song, In-Young;Park, Sung-Hae;Park, Tai-Ho
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.08a
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    • pp.68-69
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    • 2011
  • The process of charge transfer at the interface between two semiconductors or between a metal and a semiconductor plays an important role in many areas of technology. The optimization of such devices requires a good theoretical description of the interfaces involved. This, in turn, has motivated detailed mechanistic studies of interfacial charge-transfer reactions at metal/organic, organic/organic, and organic/inorganic semiconductor heterojunctions. Charge recombination of photo-induced electron with redox species such as oxidized dyes or triiodide or cationic HTM (hole transporting materials) at the heterogeneous interface of $TiO_2$ is one of main loss factors in liquid junction DSSCs or solid-state DSSCs, respectively. Among the attempts to prevent recombination reactions such as insulating thin layer and lithium ions-doped hole transport materials and introduction of co-adsorbents, although co-adsorbents retard the recombination reactions as hydrophobic energy barriers, little attention has been focused on the anchoring processes. Molecular engineering of heterogeneous interfaces by employing several co-adsorbents with different properties altered the surface properties of $TiO_2$ electrodes, resulting to the improved power conversion efficiency and long-term stability of the DSSCs. In this talk, advantages of the coadsorbent-assisted sensitization of N719 in preparation of DSSCs will be discussed.

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Nanostructured Metal Organic Framework Modified Glassy Carbon Electrode as a High Efficient Non-Enzymatic Amperometric Sensor for Electrochemical Detection of H2O2

  • Naseri, Maryam;Fotouhi, Lida;Ehsani, Ali
    • Journal of Electrochemical Science and Technology
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    • v.9 no.1
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    • pp.28-36
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    • 2018
  • Metal-organic frameworks have recently been considered very promising modifiers in electrochemical analysis due to their unique characteristics among which tunable pore sizes, crystalline ordered structures, large surface areas and chemical tenability are worth noting. In the present research, $Cu(btec)_{0.5}DMF$ was electrodeposited on the surface of glassy carbon electrode at room temperature under cathodic potential and was initially used as the active materials for the detection of $H_2O_2$. The cyclic voltammogram of $Cu(btec)_{0.5}DMF$ modified GC electrode shows distinct redox peaks potentials at +0.002 and +0.212 V in 0.1 M phosphate buffer solution (pH 6.5) corresponding to $Cu^{(II)}/Cu^{(I)}$ in $Cu(btec)_{0.5}DMF$. Acting as the electrode materials of a non-enzymatic $H_2O_2$ biosensor, the $Cu(btec)_{0.5}DMF$ brings about a promising electrocatalytic performance. The high electrocatalytic activity of the $Cu(btec)_{0.5}DMF$ modified GC electrode is demonstrated by the amperometric response towards $H_2O_2$ reduction with a wide linear range from $5{\mu}M$ to $8000{\mu}M$, a low detection limit of $0.865{\mu}M$, good stability and high selectivity at an applied potential of -0.2 V, which was higher than some $H_2O_2$ biosensors.