• Title/Summary/Keyword: Charge transfer doping

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Active Reaction Sites and Oxygen Reduction Kinetics on $La_1_{-x}Sr_xMnO_{3+\delta}$(x=0.1-0.4)/YSZ (Yttria-Stabilized Zirconia) Electrodes for Solid Oxide Fuel Cells

  • Lee, Hee Y.;Cho, Woo S.;오승모
    • Bulletin of the Korean Chemical Society
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    • v.19 no.6
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    • pp.661-666
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    • 1998
  • Active reaction sites and electrochemical O2 reduction kinetics on La_{1-x}Sr_xMnO_{3+{\delta}} (x=0.1-0.4)/YSZ (yttria-stabilized zirconia) electrodes are investigated in the temperature range of 700-900 ℃ at $Po_2=10^{-3}$-0.21 atm. Results of the steady-state polarization measurements, which are formulated into the Butler-Volmer formalism to extract transfer coefficient values, lead us to conclude that the two-electron charge transfer step to atomically adsorbed oxygen is rate-limiting. The same conclusion is drawn from the $Po_2$-dependent ac impedance measurements, where the exponent m in the relationship of $I_o$ (exchange current density) ∝ $P_{o_{2}}^m$ is analyzed. Chemical analysis is performed on the quenched Mn perovskites to estimate their oxygen stoichiometry factors (δ) at the operating temperature (700-900 ℃). Here, the observed δ turns out to become smaller as both the Sr-doping contents (x) and the measured temperature increase. A comparison between the 8 values and cathodic activity of Mn perovskites reveals that the cathodic transfer coefficients $({\alpha}_c)$ for oxygen reduction reaction are inversely proportional to δ whereas the anodic ones $({\alpha}_a)$ show the opposite trend, reflecting that the surface oxygen vacancies on Mn perovskites actively participate in the $O_2$ reduction reaction. Among the samples of x= 0.1-0.4, the manganite with x=0.4 exhibits the smallest 8 value (even negative), and consistently this electrode shows the highest ${\alpha}_c$ and the best cathodic activity for the oxygen reduction reaction.

Photocatalytic Activity of Hierarchical N doped TiO2 Nanostructures

  • Naik, Brundabana;Kim, Sun Mi;Jung, Chan Ho;Park, Jeong Young
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.669-669
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    • 2013
  • Hierarchical N doped TiO2 nanostructured catalyst with micro, meso and macro porosity have been synthesized by a facile self-formation route using ammonia and titanium isopropoxide precursor. The samples were calcined in different calcination temperature ranging from $300^{\circ}C$ to $800^{\circ}C$ at slow heating rate ($5^{\circ}C$/min) and designated as NHPT-300 to NHPT-800. $TiO_2$ nanostructured catalyst have been characterized by physico-chemical and spectroscopy methods to explore the structural, electronic and optical properties. UV-Vis diffuse reflectance spectra confirmed the red shift and band gap narrowing due to the doping of N species in TiO2 nanoporous catalyst. Hierarchical macro porosity with fibrous channel patterning was observed (confirmed from FESEM) and well preserved even after calcination at $800^{\circ}C$, indicating the thermal stability. BET results showed that micro and mesoporosity was lost after $500^{\circ}C$ calcination. The photocatalytic activity has been evaluated for methanol oxidation to formaldehyde in visible light. The enhanced photocatalytic activity is attributed to combined synergetic effect of N doping for visible light absorption, micro and mesoporosity for increase of effective surface area and light harvestation, and hierarchical macroporous fibrous structure for multiple reflection and effective charge transfer.

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Improved Electrical Properties of Graphene Transparent Conducting Films Via Gold Doping

  • Kim, Yoo-Seok;Song, Woo-Seok;Kim, Sung-Hwan;Jeon, Cheol-Ho;Lee, Seung-Youb;Park, Chong-Yun
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.08a
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    • pp.388-388
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    • 2011
  • Graphene, with its unique physical and structural properties, has recently become a proving ground for various physical phenomena, and is a promising candidate for a variety of electronic device and flexible display applications. The physical properties of graphene depend directly on the thickness. These properties lead to the possibility of its application in high-performance transparent conducting films (TCFs). Compared to indium tin oxide (ITO) electrodes, which have a typical sheet resistance of ~60 ${\Omega}/sq$ and ~85% transmittance in the visible range, the chemical vapor deposition (CVD) synthesized graphene electrodes have a higher transmittance in the visible to IR region and are more robust under bending. Nevertheless, the lowest sheet resistance of the currently available CVD graphene electrodes is higher than that of ITO. Here, we report an ingenious strategy, irradiation of MeV electron beam (e-beam) at room temperature under ambient condition,for obtaining size-homogeneous gold nanoparticle decorated on graphene. The nano-particlization promoted by MeV e-beam irradiation was investigated by transmission electron microscopy, electron energy loss spectroscopy elemental mapping, and energy dispersive X-ray spectroscopy. These results clearly revealed that gold nanoparticle with 10~15 nm in mean size were decorated along the surface of the graphene after 1.0 MeV-e-beam irradiation. The fabrication high-performance TCF with optimized doping condition showed a sheet resistance of ~150 ${\Omega}/sq$ at 94% transmittance. A chemical transformation and charge transfer for the metal gold nanoparticle were systematically explored by X-ray photoelectron spectroscopy and Raman spectroscopy. This approach advances the numerous applications of graphene films as transparent conducting electrodes.

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Interfacial Engineering of In2O3/In2S3 Heterojunction Photoanodes for Photoelectrochemical Water Oxidation

  • Bo Reum Lee;Sungkyun Choi;Woo Seok Cheon;Jin Wook Yang;Mi Gyoung Lee;So Hyeon Park;Ho Won Jang
    • Electronic Materials Letters
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    • v.18
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    • pp.391-399
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    • 2022
  • Photoelectrochemical (PEC) water splitting is one of the critical energy conversion techniques to prepare for future energy demands. Among the various trials to construct effective water splitting semiconductor photoelectrodes, In2O3/In2S3 heterostructures can be promising candidates for their advantageous properties in solar water oxidation. Herein, we synthesized In2O3 nanorods on FTO substrate through a direct glancing angle deposition method. Subsequently, the In2S3 layer was conformally coated on In2O3 nanorods through facile chemical bath deposition. As synthesized photoanodes of In2O3/In2S3 form type II junction, leading to considerable cathodic onset potential shift with the increased photocurrent density compared to pristine samples. To further enhance PEC properties, the interficial engineering strategies of the Co ion doping and the deposition of ultra-thin Al2O3 film were carried out. Co ion could facilitate the charge transfer in photoanodes through the increased surface area, and the 2 nm Al2O3 layer coated above the photoanode effectively worked as the passivation layer to stabilize the photoanodes in alkaline electrolytes environments. This work would contribute to developing efficient photoanodes through various nanoscale engineering strategies.

The Structural Stability and Electrochemical Properties of Fe Doped Li[Ni0.575Co0.1Mn0.325]O2 (Fe을 도핑한 Li[Ni0.575Co0.1Mn0.325]O2의 구조적인 안정성 및 전기화학적 특성)

  • Yang, Su-Bin;Yoo, Gi-Won;Jang, Byeong-Chan;Son, Jong-Tae
    • Journal of the Korean Electrochemical Society
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    • v.17 no.3
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    • pp.149-155
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    • 2014
  • In this study, a positive-electrode material in a lithium secondary battery $Li[Ni_{0.575}Co_{0.1}Mn_{0.325}]O_2$ was synthesized as precursor by co-precipitation. Cathode material was synthesized by adding iron. The synthesized cathode material was analyzed by scanning electron microscope and x-ray diffraction. The analysis of x-ray diffraction showed that the a-axis and c-axis is increased by doping iron. And $I_{(003)}/I_{(104)}$ is increased and $I_{(006)}+I_{(102)}/I_{(101)}$ is decreased. Through this result, it was confirmed that the structural stability is improved. And impedance measurements show that the charge transfer resistance ($R_{ct}$) is lowered by doping iron. Consequently, electrochemical properties are improved by doping iron. In particular, the cycle characteristics are improved at a high temperature condition (328 K). Structural stabilities are contributing to the cycle properties.

Electrolyte Preparation and Characteristics of La1-xSrxMnO3 for Solid Oxide Fuel Cell (고체전해질형 연료전지용 전해질 제작 및 La1-xSrxMnO3의 특성에 관한 고찰)

  • Rim, Hyung-Ryul;Lee, Ju-Seong
    • Applied Chemistry for Engineering
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    • v.7 no.1
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    • pp.9-17
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    • 1996
  • Solid oxide electrolytes of 8mol% YSZ($Y_2O_3$ stabilized zirconia) were prepared at various sintering conditions and their ionic conductivities were measured. The highest ionic conductivity of $10^{-1}S.cm^{-1}$ was obtained when the sintering temperature was 1400oC and the sintering time was 10hr. Also the cathode material, $La_{1-x}Sr_xMnO_3$ was prepared by solid state reaction method and the overpotential, electrical conductivity, and charge transfer resistance between cathode material and YSZ electrolyte were studied. It was found that the optimum doping content of Sr for La was 50mo1%.

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Novel Method to Confine Manganese Oxide Nanoparticles in Polyaniline Hollow Nanospheres and Its Supercapacitive Properties

  • Kwon, Hyemin;Lee, Jinho;Munkhbaatar, Naranchimeg;Yim, Sanggyu
    • Proceedings of the Korean Vacuum Society Conference
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    • 2014.02a
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    • pp.196.2-196.2
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    • 2014
  • Nanostructuring the electrode surface is an emerging technology to improve the performance of supercapacitors since it can facilitate charge transfer, ion diffusion and electron propagation during electrochemical process. Fabrication of the electrode consisting of two or more materials together has also been focused on since it can provide synergetic effect such as broader working potential range and enhanced capacitance. In this work, we have used polyaniline (PANi) and manganese oxide (MnO2) as electrode materials. PANi is one of the promising electrode materials due to its high electrochemical activity, high doping level and stability. MnO2 is also widely studied material for supercapacitors since it is relatively cheap and environmentally friendly. Firstly, we synthesized polystyrene nanospheres on MnO2 nanoparticles. MnO2-incorporated PANi hollow nanospheres were then fabricated by polymerizing aniline monomers on these PS nanospheres and dissolving the inner PS spheres. The surface morphology, electronic absorption and electrical conductivity of the electrode were analyzed using field-emission scanning electron microscope (FE-SEM), UV-visible spectrometer, and sheet resistivity meter, respectively. The electrochemical properties such as capacitance of the supercapacitors were also estimated using cyclic voltammetry.

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Preparation of pseudo n-type Polyaniline and Evaluation of Electrochemical Properties (가상 n형 폴리아닐린의 제조 및 전기화학적 특성평가)

  • 김래현;최선용;정건용
    • Membrane Journal
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    • v.13 no.3
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    • pp.162-173
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    • 2003
  • The pseudo n-type polyaniline was prepared by doping of camphorsulfonic acid(CSA) and dodecylbenzenesulfonic acid(DBSA) as the dopants in solvent of N-methyl-2-pyrrolidinone(NMP). The dopants in polymer structure was qualitatively analyzed using FT-IR. The influence on electrochemical properties with dopant concentration of PANI film were investigated. The electrochemical characteristics of the n-type PANI electrode that coated on ITO were evaluated by cyclic voltammetry(CV) and AC impedance method. The prepared PANI were confirmed as n-type PANI from FT-IR and CV. The charge transfer resistance of film on PANI/CSA electrode were measured as 1.14{\sim}1.09k{\mu}$by AC impedance. The charge transfer resistance of PANI/DBSA electrode decreased with increasing the mole ratio of DBSA as 27.73{\sim}8.37 k{\mu}$. The double layer capacitance of PANI/CSA electrode was showed almost constant value as $13.47{\sim}14.59 {\mu}F$ and that of PANI/DBSA electrode increased with increasing mole ratio of DBSA from 0.49 to $1.20 {\mu}F$.

Photoreduction of Carbon Dioxide using Graphene Oxide-Titanium Oxide Composite (그래핀 옥사이드와 이산화티타늄 조합을 이용한 이산화탄소의 광환원)

  • Lee, Myung-Kyu;Jang, Jun-Won;Park, Sung-Jik;Park, Jae-Woo
    • Journal of Korean Society on Water Environment
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    • v.32 no.1
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    • pp.46-51
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    • 2016
  • In this study, we synthesized a combination of graphene oxide (GO) and titanium dioxide (TiO2) and confirm that GO can be used for CO2 photoreduction. TiO2 exhibited highly efficient combination with other conventional electric charges generated by these paration phenomenon for suppression of hole-electron recombination. This improved the efficiency of CO2 photoreduction. The synthetic form of GO-TiO2 used in this study was agraphene sheet surrounded by TiO2 powder. Efficiency and stability were enhanced by combination of GO and TiO2. In a CO2 photoreduction experiment, the highest CO conversion rate was 0.652 μmol/g·h in GO10-TiO2 (2.3-fold that of pure TiO2) and the highest CH4 production rate was 0.037 μmol/g·h in GO0.1-TiO2 (2.4-fold that of pure TiO2). GO enhances photocatalytic efficiency by functioning as a support and absorbent, and enabling charge separation. With increasing GO concentration, the CH4 level decreases to~45% due to decreased transfer of electrons. In this study, TiO2 together with GO yielded a different result than the normal doping effect and selective CO2 photoreduction.

Photoelectrochemical Cell Study on Closely Arranged Vertical Nanorod Bundles of CdSe and Zn doped CdSe Films

  • Soundararajan, D.;Yoon, J.K.;Kwon, J.S.;Kim, Y.I.;Kim, S.H.;Park, J.H.;Kim, Y.J.;Park, D.Y.;Kim, B.C.;Wallac, G.G.;Ko, J.M.
    • Bulletin of the Korean Chemical Society
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    • v.31 no.8
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    • pp.2185-2189
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    • 2010
  • Closely arranged CdSe and Zn doped CdSe vertical nanorod bundles were grown directly on FTO coated glass by using electrodeposition method. Structural analysis by XRD showed the hexagonal phase without any precipitates related to Zn. FE-SEM image showed end capped vertically aligned nanorods arranged closely. From the UV-vis transmittance spectra, band gap energy was found to vary between 1.94 and 1.98 eV due to the incorporation of Zn. Solar cell parameters were obtained by assembling photoelectrochemical cells using CdSe and CdSe:Zn photoanodes, Pt cathode and polysulfide (1M $Na_2S$ + 1M S + 1M NaOH) electrolyte. The efficiency was found to increase from 0.16 to 0.22 upon Zn doping. Electrochemical impedance spectra (EIS) indicate that the charge-transfer resistance on the FTO/CdSe/polysulfide interface was greater than on FTO/CdSe:Zn/polysulfide. Cyclic voltammetry results also indicate that the FTO/CdSe:Zn/polysulfide showed higher activity towards polysulfide redox reaction than that of FTO/CdSe/polysulfide.