• Title/Summary/Keyword: electrochemical reduction

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Highly Efficient Red Emissive Heteroleptic Cyclometalated Iridium(III) Complexes Bearing Two Substituted 2-Phenylquinoxaline and One 2-Pyrazinecarboxylic Acid

  • Sengottuvelan, Nallathambi;Yun, Seong-Jae;Kim, Dae-Young;Hwang, In-Hye;Kang, Sung Kwon;Kim, Young-Inn
    • Bulletin of the Korean Chemical Society
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    • v.34 no.1
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    • pp.167-173
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    • 2013
  • A series of highly efficient red phosphorescent heteroleptic iridium(III) complexes 1-6 containing two cyclometalating 2-(2,4-substitued phenyl)quinoxaline ligands and one chromophoric ancillary ligand were synthesized: (pqx)$_2Ir$(mprz) (1), (dmpqx)$_2Ir$(mprz) (2), (dfpqx)$_2Ir$(mprz) (3), (pqx)$_2Ir$(prz) (4), (dmpqx)$_2Ir$(prz) (5), (dfpqx)$_2Ir$(prz) (6), where pqx = 2-phenylquinoxaline, dfpqx = 2-(2,4-diflourophenyl)quinoxaline, dmpqx = 2-(2,4-dimethoxyphenyl)quinoxaline, prz = 2-pyrazinecarboxylate and mprz = 5-methyl-2-pyrazinecarboxylate. The absorption, emission, electrochemical and thermal properties of the complexes were evaluated for potential applications to organic light-emitting diodes (OLEDs). The structure of complex 2 was also determined by single-crystal X-ray diffraction analysis. Complex 2 exhibited distorted octahedral geometry around the iridium metal ion, for which 2-(2,4-dimethoxyphenyl)quinoxaline N atoms and C atoms of orthometalated phenyl groups are located at the mutual trans and cis-positions, respectively. The emission spectra of the complexes are governed largely by the nature of the cyclometalating ligand, and the phosphorescent peak wavelengths can be tuned from 588 to 630 nm with high quantum efficiencies of 0.64 to 0.86. Cyclic voltammetry revealed irreversible metal-centered oxidation with potentials in the range of 1.16 to 1.89 V as well as two quasi-reversible reduction waves with potentials ranging from -0.94 to -1.54 V due to the sequential addition of two electrons to the more electron-accepting heterocyclic portion of two distinctive cyclometalated C^N ligands.

The Early Stages of Formation of the Passivation Film on Iron Electrode. Electrochemical and Automatic Ellipsometry Investigation (철전극 표면 부동화막의 생성과 초기단계의 변화)

  • In-Hyeong Yeo;Woon-Kie Paik
    • Journal of the Korean Chemical Society
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    • v.28 no.5
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    • pp.271-278
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    • 1984
  • Ellipsometric and reflectance measurements were made with magneto-optically self-nulling ellipsometer on the iron surface being passivated. The passivation was induced by abruptly changing potential of the mechanically polished high purity iron from the reduction potential to the oxidation potential in basic solutions. From the differences in the optical paramates(${\Delta},\;{\psi}$) and reflectance (R) between the reduced (film-free) and oxidized (film-covered) states, the thickness(${\tau}$) and optical constants (n, k) of the film in the early stage of its formation were computed as functions of pH and time. From the computed values, it was deduced that the properties of the anodic film did not undergo a drastic change with time which would indicate a transformation of the film before effective passivity is attained, and that the film reached its stady state within a few second. The thickness of anodic film was $14\;{\sim}\;23{\AA}$. The anodic films also seemed to have small values of optical absorption coefficient. The film formed in high pH environments had thinner and denser structure than that formed in low pH.

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The influence of preparation conditions on the electrochemical degradation of tungsten oxide thin films prepared by electron beam deposition (제작조건이 전자비임으로 제작된 텅스텐산화물 박막의 전기화학적 퇴화에 미치는 영향)

  • 이길동
    • Journal of the Korean Vacuum Society
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    • v.7 no.4
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    • pp.306-313
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    • 1998
  • The electrochromic $WO_3$thin films were prepared by using the electron-beam evaporatin technique. Flms prepared at a vacuum pressure of $10^{-4}$ mbar were found to be most stable during repeated potential cycles. The chemical stability of the film in aqueous solutions was also affected by the vacuum pressure during evaporation. The redox current and the optical properties of the degraded films were affected by the thickness of the film. The 5,000$\AA$-thick films were found to be most stable, undergoing the least degradation during the repeated coloring and bleaching cycles. The origin of the mechanism dominating the degradation during the repeated coloring and bleaching cycles was the accumulation of lithium in the film, which results in decreasing redox current. Tungsten oxide films with titanium content of about 10-15 mol% was found to be most stable, undergoing the least degradation during the repeated cycles. The origin of the mechanism dominating the least degradation during the repeated cycles was the reduction of lithium ion trapping sites in the films, which results in a increased durability.

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Preparation of Conducting Polymer PEDiTT Thin Film Using SAM Method (자기조립법을 이용한 전도성고분자 PEDiTT박막의 제조)

  • 손용근;강규식;심창용;최정식;이두연
    • Polymer(Korea)
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    • v.26 no.5
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    • pp.589-598
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    • 2002
  • thiathlophene (EDiTT) was synthesized. The yield of the synthesis was about 29%. The monomer was identified by using NMR, IR and UV/Vis spectroscopic methods. Poly (3,4-ethylenedithiathiophene) (PEDiTT) was prepared using this monomer and FeCl$_3$. The deep blue green color of the product was changed into brown color by the reduction with $N_2$H$_4$. This was soluble to common organic solvents. Spectroelectrochemistry was used to characterize the PEDiTT. NMP was the best solvent for PEDiTT. PEDiTT/NMP solution was used for making SAM type thin film of the polymer on gold electrode. Electrochemical and IR spectroscopic methods were used to identify the thin film.

Anodic Reactions at a Pb-Ag Anode in Sulfuric Acid Solutions Containing Manganese(II) (망간(II)을 함유한 황산용액에서 Pb-Ag 양극의 산화반응)

  • Lee, Man-Seung;Nicol, M.J.
    • Resources Recycling
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    • v.26 no.4
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    • pp.34-41
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    • 2017
  • The effect of Mn(II) concentration on the anodic reactions occurring on a Pb-Ag electrode in sulfuric acid solutions has been studied by potentiostatic oxidation in the potential range of 1.8 to 2.0 V. High oxidation potentials and low initial concentrations of Mn(II) resulted in higher concentrations of soluble Mn(III) ions which were obtained from spectrophotometric analysis of the solution after oxidation. $MnO_2$ was deposited on the electrode by electrochemical oxidation of Mn(II) at 1.8 and 1.9 V, while it was formed by disproportionation of Mn(III) at 2.0 V. No $PbO_2$ was formed in the presence of Mn(II) during potentiostatic oxidation treatment for two hours at 1.8 V. Chemical reduction of $PbO_2$ with Mn(II) led to a decrease in the amount of $PbO_2$ as Mn(II) concentration increased at 1.9 and 2.0 V.

Synthesis of Pentadentate Schiff Base Molybdenum(Ⅴ) Complexes and Their Electrochemical Properties in Aprotic Solvents (다섯자리 Schiff Base Molybdenum(Ⅴ) 착물들의 합성과 비수용매에서의 전기화학적 성질)

  • Kim, Seon Suk;Choe, Ju Hyeong;Choe, Yong Guk;Jeong, Byeong Gu
    • Journal of the Korean Chemical Society
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    • v.38 no.2
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    • pp.160-168
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    • 1994
  • Pentadentate Schiff base molybdenum(Ⅴ) complexes such as [Mo(Ⅴ)O(Sal-DET)(NCS)] and [Mo(Ⅴ)O(Sal-DPT)(NCS)] were synthesized by Sabat method. The structure of these complexes were identified by elemental analysis, spectroscopy, and thermogravimetric analysis(T.G.A.). It was found that the mole ratio of Schiff base ligand to the complexes was found to be 1 : 1. The redox processes of the complexes were investigated by cyclic voltammetric and differential pulse polarographic technique in nonaqueous solvent containing 0. 1 M tetraethyl ammonium perchlorate(TEAP) as supporting electrolyte at glassy carbon electrode. It was found that diffusion controlled reduction processes of four steps with one electron were 2Mo(Ⅴ)$\rightleftarrow^{e-}$ Mo(Ⅴ)Mo(Ⅳ) $\longrightarrow^{e-}$ 2Mo(Ⅳ), Mo(Ⅳ) $\longrightarrow^{e-}$ Mo(Ⅲ) $\longrightarrow^{e-}$ Mo(Ⅱ)

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In situ Structural Investigation of Iron Phthalocyanine Monolayer Adsorbed on Electrode Surface by X-ray Absorption Fine Structure

  • Kim, Seong Hyeon;Toshiaki Ohta;Gang, Gwang Hun
    • Bulletin of the Korean Chemical Society
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    • v.21 no.6
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    • pp.588-594
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    • 2000
  • Structural changes of an iron phthalocyanine (FePC) monolayer induced by adsorption and externally applied potential on high area carbon surface have been investigated in situ by iron K-edge X-ray absorption fine structure (XAFS) in 0.5 M $H_2S0_4.$ Fine structures shown in the X-ray absorption near edge structure (XANES) for microcrystalline FePC decreased upon adsorption and further diminished under electrochemical conditions. Fe(II)PC(-2) showed a 1s ${\rightarrow}$ 4p transition as poorly resolved shoulder to the main absorption edge rather than a distinct peak and a weak 1s ${\rightarrow}$ 3d transition. The absorption edge position measured at half maximum was shifted from 7121.8 eV for Fe(lI)PC(-2) to 7124.8 eV for $[Fe(III)PC(-2)]^+$ as well as the 1s ${\rightarrow}$ 3d pre-edge peak being slightly enhanced. However, essentially no absorption edge shift was observed by the 1-electron reduction of Fe(Il)PC(-2), indicating that the species formed is $[Fe(II)PC(-3)]^-$. Structural parameters were obtained by analyzing extended X-ray absorption fine structure (EXAFS) oscillations with theoretical phases and amplitudes calculated from FEFF 6.01 using multiple-scattering theory. When applied to the powder FePC, the average iron-to-phthalocyanine nitrogen distance, d(Fe-$N_p$) and the coordination number were found to be 1.933 $\AA$ and 3.2, respectively, and these values are the same, within experimental error, as those reported ( $1.927\AA$ and 4). Virtually no structural changes were found upon adsorption except for the increased Debye-Wailer factor of $0.005\AA^2$ from $0.003\AA^2.$ Oxidation of Fe(II)PC(-2) to $[Fe(III)PC(-2)]^+$ yielded an increased d(Fe-Np) (1 $.98\AA)$ and Debye-Wailer factor $(0.005\AA^2).$ The formation of $[Fe(II)PC(-3)]^-$, however, produced a shorter d(Fe-$N_p$) of $1.91\AA$ the same as that of crystalline FePC within experimental error, and about the same DebyeWaller $factor(0.006\AA^2)$.

Improved structures of stainless steel current collector increase power generation of microbial fuel cells by decreasing cathodic charge transfer impedance

  • Nam, Taehui;Son, Sunghoon;Kim, Eojn;Tran, Huong Viet Hoa;Koo, Bonyoung;Chai, Hyungwon;Kim, Junhyuk;Pandit, Soumya;Gurung, Anup;Oh, Sang-Eun;Kim, Eun Jung;Choi, Yonghoon;Jung, Sokhee P.
    • Environmental Engineering Research
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    • v.23 no.4
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    • pp.383-389
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    • 2018
  • Microbial fuel cell (MFC) is an innovative environmental and energy system that converts organic wastewater into electrical energy. For practical implementation of MFC as a wastewater treatment process, a number of limitations need to be overcome. Improving cathodic performance is one of major challenges, and introduction of a current collector can be an easy and practical solution. In this study, three types of current collectors made of stainless steel (SS) were tested in a single-chamber cubic MFC. The three current collectors had different contact areas to the cathode (P $1.0cm^2$; PC $4.3cm^2$; PM $6.5cm^2$) and increasing the contacting area enhanced the power and current generations and coulombic and energy recoveries by mainly decreasing cathodic charge transfer impedance. Application of the SS mesh to the cathode (PM) improved maximum power density, optimum current density and maximum current density by 8.8%, 3.6% and 6.7%, respectively, comparing with P of no SS mesh. The SS mesh decreased cathodic polarization resistance by up to 16%, and cathodic charge transfer impedance by up to 39%, possibly because the SS mesh enhanced electron transport and oxygen reduction reaction. However, application of the SS mesh had little effect on ohmic impedance.

Development of Micro-Tubular Perovskite Cathode Catalyst with Bi-Functionality on ORR/OER for Metal-Air Battery Applications

  • Jeon, Yukwon;Kwon, Ohchan;Ji, Yunseong;Jeon, Ok Sung;Lee, Chanmin;Shul, Yong-Gun
    • Korean Chemical Engineering Research
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    • v.57 no.3
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    • pp.425-431
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    • 2019
  • As rechargeable metal-air batteries will be ideal energy storage devices in the future, an active cathode electrocatalyst is required with bi-functionality on both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) during discharge and charge, respectively. Here, a class of perovskite cathode catalyst with a micro-tubular structure has been developed by controlling bi-functionality from different Ru and Ni dopant ratios. A micro-tubular structure is achieved by the activated carbon fiber (ACF) templating method, which provides uniform size and shape. At the perovskite formula of $LaCrO_3$, the dual dopant system is successfully synthesized with a perfect incorporation into the single perovskite structure. The chemical oxidation states for each Ni and Ru also confirm the partial substitution to B-site of Cr without any changes in the major perovskite structure. From the electrochemical measurements, the micro-tubular feature reveals much more efficient catalytic activity on ORR and OER, comparing to the grain catalyst with same perovskite composition. By changing the Ru and Ni ratio, the $LaCr_{0.8}Ru_{0.1}Ni_{0.1}O_3$ micro-tubular catalyst exhibits great bi-functionality, especially on ORR, with low metal loading, which is comparable to the commercial catalyst of Pt and Ir. This advanced catalytic property on the micro-tubular structure and Ru/Ni synergy effect at the perovskite material may provide a new direction for the next-generation cathode catalyst in metal-air battery system.

Synthesis and Characteristics of Pd/r-TiO2 Nanotube Arrays Hetrojunction Photocatalyst (Pd/r-TiO2 나노튜브 이종결합 광촉매의 합성과 특성)

  • Lee, Jong-Ho;Lee, Young-Ki;Kim, Young-Jig;Jang, Kyung-Wook;Oh, Han-Jun
    • Korean Journal of Materials Research
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    • v.32 no.1
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    • pp.14-22
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    • 2022
  • To improve light absorption ability in the visible light region and the efficiency of the charge transfer reaction, Pd nanoparticles decorated with reduced TiO2 nanotube photocatalyst were synthesized. The reduced TiO2 nanotube photocatalyst was fabricated by anodic oxidation of Ti plate, followed by an electrochemical reduction process using applied cathodic potential. For TiO2 photocatalyst electrochemically reduced using an applied voltage of -1.3 V for 10 min, 38% of Ti4+ ions on TiO2 surface were converted to Ti3+ ion. The formation of Ti3+ species leads to the decrease in the band gap energy, resulting in an increase in the light absorption ability in the visible range. To obtain better photocatalytic efficiency, Pd nanoparticles were decorated through photoreduction process on the surface of reduced TiO2 nanotube photocatalyst (r10-TNT). The Pd nanoparticles decorated with reduced TiO2 nanotube photocatalyst exhibited enhanced photocurrent response, and high efficiency and rate constant for aniline blue degradation; these were ascribed to the synergistic effect of the new electronic state of the TiO2 band gap energy induced by formation of Ti3+ species on TiO2, and by improvement of the charge transfer reaction.