• Title/Summary/Keyword: Charge density

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Anomalous Luminescence and Emission Quenching Behaviors of Tris(2,2$^\prime$-bipyridine)Ruthenium(Ⅱ) in Poly(methacrylic acid) Solutions$^1$

  • Park, Joon-Woo;Paik, Young-Hee
    • Bulletin of the Korean Chemical Society
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    • v.7 no.2
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    • pp.137-142
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    • 1986
  • The luminescence spectra of $Ru(bpy)_3^{2+}$ in poly(methacrylic acid) (PMA) solutions varied sensitively with pH. At pH < 5.5, the emission intensity increased with pH up to 4 times, while it decreased with pH beyond the pH. The enhanced emission intensity was accompanied by blue-shift of the emission maxima as much as 15 nm. The enhancement of emission intensity was attributed to the restricted rotational mobility of ligand of the cation bound to densely coiled PMA molecules at pH < 5.5. The sharp decrease in emission intensity with increasing pH near pH 5.6 was accounted for conformational transition of the polymer to more extended structure, which was also revealed in viscosity measurement. The enhancement of emission intensity became higher as NaCl concentration of the solution increased. The binding constant of $Ru(bpy)_3^{2+}$ with two carboxylate groups of PMA was calculated as $2{\times}10^5\;M^{-1}$ in 0.1 M NaCl at pH 5.2. The pH dependence of luminescence quenching rate of $Ru(bpy)_3^{2+}$ by $Cu^{++}$ also showed maximum near pH 5, and the rate was more than $10^3$ times higher than that in water, whereas the maximum enhancement of quenching rate (about 20 times) in poly(acrylic acid) (PAA) solution occurred at pH 4.5. On the other hand, the pH dependence for neutral water soluble nitrobenzene (NB) exhibited opposite trend to that of $Cu^{++}$. The quenching constant vs pH curve for $MV^{++}$ was composite of those for $Cu^{++}$ and NB. The anomalous high quenching rate for $Cu^{++}$ in PMA solution at pH < 5.5 was attributed to the binding of $Ru(bpy)_3^{2+}$ and $Cu^{++}$ to the same region of PMA, when it conforms densely coiled structure in the pH range. The observation of mininium quenching rate for NB near pH 5.5 indicated that the $Ru(bpy)_3^{2+}$ bound to the densely coiled PMA is not accessible by NB, which is in bulk water phase. The composite nature of the pH dependence of quenching rate for $MV^{++}$ in PMA solution was attributed to the smaller binding affinity of the cation to PMA, compared to that of $Cu^{++}$. The sharp, cooperative conformational transition with pH observed in PMA was not revealed in PAA. But, the pH dependence of quenching rates in this polymer reflected increased charge density and, thus, binding of cations to the polymer, and expansion of the polymer chain with pH.

Performance Evaluation of Aqueous Redox Flow Battery using Quinone Redox Couple Dissolved in Ammonium Chloride Electrolyte (염화암모늄 전해질에 포함된 퀴논 레독스 활물질 조합을 이용한 수계 레독스 흐름 전지 성능 평가)

  • Lee, Wonmi;Chung, Kun Yong;Kwon, Yongchai
    • Korean Chemical Engineering Research
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    • v.57 no.2
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    • pp.239-243
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    • 2019
  • In this study, anthraquinone-2,7-disulfonic acid (2,7-AQDS) is used as negative active material and Tiron is used as positive active material for aqueous redox flow battery (RFB). In previous results that used the 2,7-AQDS and Tiron, sulfuric acid ($H_2SO_4$) was a supporting electrolyte. However, in this study, ammonium chloride ($NH_4Cl$) is suggested as the electrolyte for the first time. By changing the supporting electrolyte from $H_2SO_4$ to $NH_4Cl$, the cell voltage of RFB is improved from 0.76 V to 1.01 V. To investigate the effect of $NH_4Cl$ supporting electrolyte of the performance of RFB, the full-cell tests of RFB using 2,7-AQDS and Tiron that are dissolved in $NH_4Cl$ supporting electrolyte are carried out, while cut-off voltage range is a main parameter to determine their performance. When the cut-off voltage range is 0.2~1.6 V, the hydrogen evolution occurs during charging step. To address the side reaction effect, the cut-off voltage range is changed to 0.2~1.2 V. When the revised cut-off voltage range is used and the current density of $40mA/cm^2$ is applied, hydrogen evolution is not observed and the optimal RFB shows the charge efficiency of 99% and discharge capacity of 3.3 Ah/L at 10cycle.

Nanolayered CuWO4 Decoration on Fluorine-Doped SnO2 Inverse Opals for Solar Water Oxidation

  • Cho, Ha Eun;Yun, Gun;Arunachalam, Maheswari;Ahn, Kwang-Soon;Kim, Chung Soo;Lim, Dong-Ha;Kang, Soon Hyung
    • Journal of Electrochemical Science and Technology
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    • v.9 no.4
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    • pp.282-291
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    • 2018
  • The pristine fluorine-doped $SnO_2$ (abbreviated as FTO) inverse opal (IO) was developed using a 410 nm polystyrene bead template. The nanolayered copper tungsten oxide ($CuWO_4$) was decorated on the FTO IO film using a facile electrochemical deposition, subsequently followed by annealing at $500^{\circ}C$ for 90 min. The morphologies, crystalline structure, optical properties and photoelectrochemical characteristics of the FTO and $CuWO_4$-decorated FTO (briefly denoted as $FTO/CuWO_4$) IO film were investigated by field emission scanning electron microscopy, X-ray diffraction, UV-vis spectroscopy and electrochemical impedance spectroscopy, showing FTO IO in the hexagonally closed-pack arrangement with a pore diameter and wall thickness of about 300 nm and 20 nm, respectively. Above this film, the $CuWO_4$ was electrodeposited by controlling the cycling number in cyclic voltammetry, suggesting that the $CuWO_4$ formed during 4 cycles (abbreviated as $CuWO_4$(4 cycles)) on FTO IO film exhibited partial distribution of $CuWO_4$ nanoparticles. Additional distribution of $CuWO_4$ nanoparticles was observed in the case of $FTO/CuWO_4$(8 cycles) IO film. The $CuWO_4$ layer exhibits triclinic structure with an indirect band gap of approximately 2.5 eV and shows the enhanced visible light absorption. The photoelectrochemical (PEC) behavior was evaluated in the 0.5 M $Na_2SO_4$ solution under solar illumination, suggesting that the $FTO/CuWO_4$(4 cycles) IO films exhibit a photocurrent density ($J_{sc}$) of $0.42mA/cm^2$ at 1.23 V vs. reversible hydrogen electrode (RHE, denoted as $V_{RHE}$), while the FTO IO and $FTO/CuWO_4$(8 cycles) IO films exhibited a $J_{sc}$ of 0.14 and $0.24mA/cm^2$ at $1.23V_{RHE}$, respectively. This difference can be explained by the increased visible light absorption by the $CuWO_4$ layer and the favorable charge separation/transfer event in the cascading band alignment between FTO and $CuWO_4$ layer, enhancing the overall PEC performance.

Effect of O2 Plasma Treatment on Electrochemical Performance of Supercapacitors Fabricated with Polymer Electrolyte Membrane (고분자 전해질막으로 제조한 슈퍼커패시터의 전기화학적 특성에 대한 산소 플라즈마 처리 영향)

  • Moon, Seung Jae;Kim, Young Jun;Kang, Du Ru;Lee, So Youn;Kim, Jong Hak
    • Membrane Journal
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    • v.32 no.1
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    • pp.43-49
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    • 2022
  • Solid-state supercapacitors with high safety and robust mechanical properties are attracting global attention as next-generation energy storage devices. As an electrode of a supercapacitor, an economical carbon-based electrode is widely used. However, when an aqueous electrolyte is introduced, the charge transfer resistance increases because the interfacial contact between the hydrophobic electrode surface and aqueous electrolyte is not good. In this regard, we propose a method to obtain higher electrochemical performance based on improved interfacial properties by treating the electrode surface with oxygen plasma. The surface hydrophilization induced by the enriched oxygen functionalities was confirmed by the contact angle measurement. As a result, the degree of hydrophilization was easily adjusted by controlling the power and duration of the oxygen plasma treatment. As the electrolyte of the supercapacitor, PVA/H3PO4, which is a typical solid-state aqueous electrolyte, was used. Free-standing membranes of PVA/H3PO4 electrolyte were prepared and then pressed onto the electrode. The optimal condition was to perform oxygen plasma treatment for 5 seconds with a low power of 15 W, and the energy density of the supercapacitor increased by about 8%.

The Effect of Mg/W Addition on the Metal-insulator Transition of VO2 Using Spark Plasma Sintering (통전활성소결법으로 제조한 VO2의 금속-절연체 전이 특성에 W와 Mg 첨가가 미치는 영향)

  • Jin, Woochan;Kim, Youngjin;Park, Chan;Jang, Hyejin
    • Journal of the Microelectronics and Packaging Society
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    • v.29 no.4
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    • pp.63-69
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    • 2022
  • Vanadium dioxide shows a unique and interesting property of metal-insulator transition, which has attracted great attention from the viewpoints of fundamental materials science and industrial applications. In this study, the effect of Mg and W addition on the metal-insulator transition of VO2 were investigated for the bulk materials that are prepared by spark plasma sintering. The X-ray diffraction analysis of the sintered specimens revealed that the lattice parameters barely change, and the secondary phases are present. The transition temperature of MIT appears in the range of 64.2-64.6℃, regardless of the impurity element and content. On the other hand, the addition of Mg and W alters the electrical conductivity, i.e., the electrical conductivity increases by a factor of up to 2.4 or decrease by a factor of up to 57.4 depending on the impurity type and its content. The thermal conductivity showed the values of 1.8~2.5 W/m·K below the transition temperature, and the values of 1.9~2.8 W/m·K above the transition temperature. These changes in electrical and thermal conductivities can be attributed to the combination of the change in charge carrier density, the impurities as scattering centers, and the change in microstructures.

Characteristics of the ( Pb, La ) $TiO_3$ Thin Films with Pb/La Compositions (Pb/La 조성에 따른 ( Pb, La ) $TiO_3$ 박막의 특성 변화)

  • Kang, Seong-Jun;Joung, Yang-Hee;Yoon, Yung-Sup
    • Journal of the Korean Institute of Telematics and Electronics D
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    • v.36D no.1
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    • pp.29-37
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    • 1999
  • In this study, we have prepared PLT thin films having various La concentrations by using sol-gel method and studied on the effect of La concentration on the electrical properties of PLT thin films. As the La concentration increases from 5mol% to 28mol%, the dielectric constant at 10kHz increases from 428 to 761, while the loss tangent decreases from 0.063 to 0.024. Also, the leakage current density at 150kV/cm has a tendency to decrease from 6.96${\mu}A/cm^2$ to 0.79${\mu}A/cm^2$. In the result of hysteresis loops of PLT thin films, the remanent polariation and the coercive field decrease from 9.55${\mu}C/cm^2$ to 1.10${\mu}C/cm^2$ and from 46.4kV/cm to 13.7kV/cm, respectively. With the result of the fatigue test on the PLT thin films, we have found that the fatigue properties are improved remarkably as the La concentration increases from 5 mol% to 28mol%. In particular, the PLT28) has paraelectric phase and its charge storage clensity and leakage current density at 5V are 134fC/${\mu}cm^2$ and 1.01${\mu}A/cm^2$, respectively. The remanent polarization and coercive field of the PLT(10) film are 6.96${\mu}C/cm^2$ and 40.2kV/cm, respectively. After applying of $10^9$ square pulses with ${\pm}5V$, the remanent polarilzation of the PLT(10) film decreases about 20% from the initial state. In the results, we conclude that the 10mol% and the 28mol% La doped PLT thin films are very suitable for the capacitor dielectrics of new generation of DRAM and NVFRAM respecitively.

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Associations between Characteristics of Green Spaces, Physical Activity and Health - Focusing on the Case Study of Changwon City - (공원녹지의 특성과 신체활동 및 건강의 상호관련성 - 창원시를 대상으로 -)

  • Baek, Su-Kyeongq;Park, Kyung-Hun
    • Journal of the Korean Institute of Landscape Architecture
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    • v.42 no.3
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    • pp.1-12
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    • 2014
  • Urban Green space takes charge of the important role for the physical activity and promotion of health to the residents. Therefore, this study is trying to examine the relationship between the various characteristics of green space and green space usage for physical activity and health promotion. A questionnaire survey was conducted to obtain the information about patterns of green space usage and perceived neighborhood environments for the residents living in Changwon-si, Gyeongsangnam-do(n=541). Geographic Information System(GIS) was used to construct spatial data about green space accessibility and physical neighborhood environments. A Multiple Linear Regression model was used to examine the association between the characteristics of green space and physical activity, perceived health status and BMI(Body Mass Index). The study results revealed that the residents' physical activities are positively and directly influenced by the number of available public parks and green spaces in the vicinity(${\leq}200m$). The frequency at which residents witness others exercising nearby or the perceived abundance of low-cost gym facilities also factor as positive influences. The closer to the park, the higher the number of parks and area of green spaces, the more comfortable the walk thereto and the denser the neighboring residential area distribution, the perceived health level was found to be the more positively influenced. Further, it was verified that BMI is correlated with the number of public parks and green spaces within 400 m of the resident's home as well as the safety of walkways, the density of neighboring residential areas, the ratio of road, and the density of crosswalk. The significant multiple regression models between the characteristics of green spaces and physical activities and perceived health level were extracted within the significance level of 10%. This study will contribute to provide better understanding the ways in which green space and neighborhood characteristics are associated with physical activity and health. The result of this research will be available in the landscape architecture plan aimed at improving the use of green space for physical activity and reducing obesity.

A First-principles Study on the Effects on Magnetism of Si Impurity in BCC Fe by Considering Spin-orbit Coupling (스핀-궤도 상호작용을 고려한 Si 불순물이 BCC Fe의 자성에 미치는 영향에 대한 제일원리연구)

  • Rahman, Gul;Kim, In-Gee;Chang, Sam-Kyu
    • Journal of the Korean Magnetics Society
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    • v.18 no.6
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    • pp.211-216
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    • 2008
  • The effects of Si impurity on electronic structures and magnetism of bcc Fe are investigated by using a first-principles method by considering spin-orbit coupling. In order to describe the Si impurity, a 27 atomic bcc Fe supercell has been considered. The Kohn-Sham equation was solved in terms of the all-electron full-potential linearized augmented plane wave (FLAPW) method within the generalized gradient approximation (GGA). The effects of spin-orbit coupling were calculated self-consistently by considering spin-diagonal terms based on second variation method. For the ferromagnetic (FM) state without considering SOC, the spin magnetic moment of the Si impurity was calculated to be $-0.143{\mu}B$, while the magnetic moments of Fe atoms were calculated to be $2.214{\mu}B$, $2.327{\mu}B$, and $2.354{\mu}B$ in away from the Si atom, respectively. However, the FM state with considering SOC, the spin magnetic moment of the Si impurity was calculated to be $-0.144{\mu}B$, which is not affected significantly by SOC, but the spin magnetic moments of Fe atoms were calculated $2.189{\mu}B$, $2.310{\mu}B$, and $2.325{\mu}B$, respectively, which are much reduced value compared to those of the FM state without SOC. Comparing the total charge density and spin density, those features are thought to be originated by the screening distortions of the Fe $t_{2g}$ orbital, which can be obtained by considering SOC.

Effect of Terephthalaldehyde to Facilitate Electron Transfer in Heme-mimic Catalyst and Its Use in Membraneless Hydrogen Peroxide Fuel Cell (테레프탈알데하이드의 전자전달 강화효과에 따른 헴 단백질 모방 촉매의 성능 향상 및 이를 이용한 비분리막형 과산화수소 연료전지)

  • Jeon, Sieun;An, Heeyeon;Chung, Yongjin
    • Korean Chemical Engineering Research
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    • v.60 no.4
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    • pp.588-593
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    • 2022
  • Terephthalaldehyde (TPA) is introduced as a cross liker to enhance electron transfer of hemin-based cathodic catalyst consisting of polyethyleneimine (PEI), carbon nanotube (CNT) for hydrogen peroxide reduction reaction (HPRR). In the cyclic voltammetry (CV) test with 10 mM H2O2 in phosphate buffer solution (pH 7.4), the current density for HPRR of the suggested catalyst (CNT/PEI/hemin/PEI/TPA) shows 0.2813 mA cm-2 (at 0.2 V vs. Ag/AgCl), which is 2.43 and 1.87 times of non-cross-linked (CNT/PEI/hemin/PEI) and conventional cross liker (glutaraldehyde, GA) used catalyst (CNT/PEI/hemin/PEI/GA), respectively. In the case of onset potential for HPRR, that of CNT/PEI/hemin/PEI/TPA is observed at 0.544 V, while those of CNT/PEI/hemin/PEI and CNT/PEI/hemin/PEI/GA are 0.511 and 0.471 V, respectively. These results indicate that TPA plays a role in facilitating electron transfer between the electrodes and substrates due to the π-conjugated cross-linking bonds, whereas conventional GA cross-linker increases the overpotential by interrupting electron and mass transfer. Electrochemical impedance spectroscopy (EIS) results also display the same tendency. The charge transfer resistance (Rct) of CNT/PEI/hemin/PEI/TPA decreases about 6.2% from that of CNT/PEI/hemin/PEI, while CNT/PEI/hemin/PEI/GA shows the highest Rct. The polarization curve using each catalyst also supports the superiority of TPA cross liker. The maximum power density of CNT/PEI/hemin/PEI/TPA (36.34±1.41 μWcm-2) is significantly higher than those of CNT/PEI/hemin/PEI (27.87±0.95 μWcm-2) and CNT/PEI/hemin/PEI/GA (25.57±1.32 μWcm-2), demonstrating again that the cathode using TPA has the best performance in HPRR.

Synthesis of LSX Zeolite and Characterization for Nitrogen Adsorption (LSX 제올라이트의 합성 및 질소 흡착 특성)

  • Hong, Seung Tae;Lee, Jung-Woon;Hong, Hyung Phyo;Yoo, Seung-Joon;Lim, Jong Sung;Yoo, Ki-Pung;Park, Hyung Sang
    • Korean Chemical Engineering Research
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    • v.45 no.2
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    • pp.160-165
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    • 2007
  • The synthesis and the characterization of Low Silica X (LSX) zeolite for nitrogen adsorption have been studied. The performance of LSX zeolite for nitrogen adsorption was compared to that of the commercial zeolite. The $Na_2O/(Na_2O+K_2O)$ ratio in the gel and the crystallization time were fixed as the synthetic factor. The LSX zeolite was formed at the $Na_2O/(Na_2O+K_2O)$ ratio of 0.75. The formation of LSX zeolite was confirmed by XRD and SEM. The Si/Al ratio was investigated by using XRF and FT-IR. The synthesized LSX zeolite showed a lower Si/Al ratio than the NaY and NaX zeolites although they have a same faujasite structure. The Si/Al ratio of the LSX zeolite converged close to 1. 1A (Li, Na, K) and 2A (Mg, Ca, Ba) group elements were ion-exchanged to the LSX zeolite. As the charge density of cation rises, the amount of nitrogen adsorbed increased. $Li^+$ ion-exchanged LSX zeolite showed the highest nitrogen adsorption weight. When the Li/Al ratio was over 0.65, nitrogen adsorption increased remarkably. $Li^+$ ions located on the supercage (site III, III') in the LSX zeolite played a role as nitrogen adsorption sites. When the $Ca^{2+}$ ions were added to the LiLSX zeolite by ion-exchange method, the performance for nitrogen adsorption increased more. The performance for the nitrogen adsorption was the highest at the Ca/Al ratio of 0.26. Nitrogen adsorption capacity of LiCaLSX (Ca/Al=0.26) zeolite was superior to the commercial NaX zeolite.