• Title/Summary/Keyword: Energy/electron transfer

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Photoelectrochemical Water Oxidation and $CO_2$ Conversion for Artificial Photosynthesis

  • Park, Hyunwoong
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.08a
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    • pp.70-70
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    • 2013
  • As the costs of carbon-footprinetd fuels grow continuously and simultaneously atmospheric carbon dioxide concentration increases, solar fuels are receiving growing attention as alternative clean energy carriers. These fuels include molecular hydrogen and hydrogen peroxide produced from water, and hydrocarbons converted from carbon dioxide. For high efficiency solar fuel production, not only light absorbers (oxide semiconductors, Si, inorganic complexes, etc) should absorb most sunlight, but also charge separation and interfacial charge transfers need to occur efficiently. With this in mind, this talk will introduce the fundamentals of solar fuel production and artificial photosynthesis, and then discuss in detail on photoelectrochemical (PEC) water splitting and CO2 conversion. This talk largely divides into two section: PEC water oxidation and PEC CO2 reduction. The former is very important for proton-coupled electron transfer to CO2. For this oxidation, a variety of oxide semiconductors have been tested including TiO2, ZnO, WO3, BiVO4, and Fe2O3. Although they are essentially capable of oxidizing water into molecular oxygen, the efficiency is very low primarily because of high overpotentials and slow kinetics. This challenge has been overcome by coupling with oxygen evolving catalysts (OECs) and/or doping donor elements. In the latter, surface-modified p-Si electrodes are fabricated to absorb visible light and catalyze the CO2 reduction. For modification, metal nanoparticles are electrodeposited on the p-Si and their PEC performance is compared.

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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.

Improved Electrical and Optical Properties of ITO Films by Using Electron Beam Irradiated Sputter

  • Wie, Sung Min;Kwak, Joon Seop
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.407-408
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    • 2013
  • Thin transparent conductive oxides (TCOs) having a thickness lower than 30 nm have been widely usedin touch screen panels. However the resistivity of the TCO films significantly increases as the thickness decreases, due to the poor crystallinity at very thin thickness of TCO films. In this study, we have investigated the effect of electron beam irradiation during the sputtering on the electrical properties and transmittance of 30 nm-thick ITO films, which have a different SnO2 atomic percent, prepared by magnetron sputtering at room temperature. Fig. 1 shows the variation of resistivity of ITO films with a different SnO2 atomic percent for both the normal ITO films and electron beam irradiated ITO films. As shows in Fig. 1, the electron beam irradiation to the ITO (SnO2 weight percent 10%) films during the sputtering resulted in a significantly decreased in resistivity from $7.4{\times}10^{-4}{\Omega}-cm$ to $1.5{\times}10^{-4}{\Omega}-cm$ and it also increased in transmittance from 84% to 88% at a wavelength of 550 nm. These results can be attributed to energy transfer from electron to ad-atoms of ITO films during the electron beam irradiated sputtering, which can enhance the crystallinity of 30 nm-thick ITO films. It is strongly indicate that electron beam irradiation can greatly improve the electrical properties and transmittance of very thin ITO films for touch screen panels, flexible displays and solar cells.

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Electrochemical Studies of Light Lantanide Complexes (Part 1) (가벼운 란탄족 원소 착물의 전기화학적 연구 (제 1 보))

  • Kang Sam-Woo;Park Chong-Min;Chang Choo-Hawn;Do Lee-Mi;Suh Moo-Yul
    • Journal of the Korean Chemical Society
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    • v.37 no.1
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    • pp.83-91
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    • 1993
  • The eletrochemical behavior of light lanthanide complexes has been investigated by several electrochemical techniques in alkaline solutions. The composition of the complexes was determined by spectrophotometric method to be 1 : 1 and reduction mechanism was two steps 1 electron transfer reaction. The half wave potential of first peak depended on pH and cathodic current showed remarkably adsorptive properties. The results of DC and CV investigation demonstrated the quise-reversible nature of the electron transfer. The anion radical formed after first one electron reduction process, dimerizes to form dimer. The apparent irreversible behavior of the second wave is a result of the existence of a fast protonation following the second electron transfer. An exhaustive electrolysis was carried out at controlled potential of -1.80 V, deep blue color of the solution became progressively weaker, and then the solution became colorless solution. The final product of an exhaustive electrolysis is electro-inactive. The appearance of four steps may be explained by the fact the reduction of Ln-OCP elucidated ECEC mechanism.

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Electrochemical oxidation-reduction and determination of urea at enzyme free PPY-GO electrode

  • Mudila, Harish;Prasher, Parteek;Rana, Sweta;Khati, Beena;Zaidi, M.G.H.
    • Carbon letters
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    • v.26
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    • pp.88-94
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    • 2018
  • This manuscript explains the effective determination of urea by redox cyclic voltammetric analysis, for which a modified polypyrrole-graphene oxide (PPY-GO, GO 20% w/w of PPY) nanocomposite electrode was developed. Cyclic voltammetry measurements revealed an effective electron transfer in 0.1 M KOH electrolytic solution in the potential window range of 0 to 0.6 V. This PPY-GO modified electrode exhibited a moderate electrocatalytic effect towards urea oxidation, thereby allowing its determination in an electrolytic solution. The linear dependence of the current vs. urea concentration was reached using square-wave voltammetry in the concentration range of urea between 0.5 to $3.0{\mu}M$ with a relatively low limit of detection of $0.27{\mu}M$. The scanning electron microscopy was used to characterize the morphologies and properties of the nanocomposite layer, along with Fourier transform infrared spectroscopy. The results indicated that the nanocomposite film modified electrode exhibited a synergistic effect, including high conductivity, a fast electron-transfer rate, and an inherent catalytic ability.

Hydrogen Evolution from Biological Protein Photosystem I and Semiconductor BiVO4 Driven by Z-Schematic Electron Transfer

  • Shin, Seonae;Kim, Younghye;Nam, Ki Tae
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.08a
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    • pp.251.2-251.2
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    • 2013
  • Natural photosynthesis utilizes two proteins, photosystem I and photosystem II, to efficiently oxidize water and reduce NADP+ to NADPH. Artificial photosynthesis which mimics this process achieve water splitting through a two-step Z-schematic water splitting process using man-made synthetic materials for hydrogen fuel production. In this study, Z-scheme system was achieved from the hybrid materials which composed of hydrogen production part as photosystem I protein and water oxidizing part as semiconductor BiVO4. Utilizing photosystem I as the hydrogen evolving part overcomes the problems of existing hydrogen evolving p-type semiconductors such as water instability, expensive cost, few available choices and poor red light (>600 nm) absorbance. Some problems of photosystem II, oxygen evolving part of natural photosynthesis, such as demanding isolation process and D1 photo-damage can also be solved by utilizing BiVO4 as the oxygen evolving part. Preceding research has not suggested any protein-inorganic-hybrid Z-scheme composed of both materials from natural photosynthesis and artificial photosynthesis. In this study, to realize this Z-schematic electron transfer, diffusion step of electron carrier, which usually degrades natural photosynthesis efficiency, was eliminated. Instead, BiVO4 and Pt-photosystem I were all linked together by the mediator gold. Synthesized all-solid-state hybrid materials show enhanced hydrogen evolution ability directly from water when illuminated with visible light.

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Substituent Effects and Correlations of Electrochemical Behaviors with Molecular Orbital Calculation of Thioxantone DerivativesⅠ

  • 곽경도;서무룡;하광수;백우현
    • Bulletin of the Korean Chemical Society
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    • v.19 no.5
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    • pp.527-530
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    • 1998
  • This paper presents the electrochemistry and molecular orbital (MO) picture of a series of conformationally-restricted thioxantone derivatives. A series of $C_2-substituted$ thioxanthones were examined to probe the electronic influence of the substituent on the electrooxidation and electroreduction sites (i.e., on the electron densities at the 10-and 9-positions), respectively. In the presence of "electrophoric" groups such as C=O and S, characteristic electrochemical reduction and oxidation responses are observed. The electrochemical reaction was diffusion-controlled, because the $I_p/{\upsilon}^{1/2}$ ratio was constant for the anodic and cathodic wave of thioxantone derivatives. These substituent effects are presented in terms of correlations of oxidation (or reduction) potentials with the highest occupied molecular orbital (HOMO), or lowest unoccupied molecular orbital (LUMO) energies, respectively. There is good correlation between energies of the HOMO vs. $E_{pa}^{(+)}$ and energies of the LUMO vs. $E_{pc}^{(-)}$. Frontier Molecular Orbital (FMO) is changed by the functional group of thioxanthones. FMO energy level was offered us the information about the electron transfer direction, and the coefficient of FMO was offered the information about the electron transfer position. Sulfur atom has an important effect on oxidation potential, $E_{pa}^{(+)}$ and the carbonyl carbon has an important effect on reduction potential, $E_{pc}^{(-)}$. Therefore we were appreciated that the contribution of sulfur atom for the $E_{pa}^{(+)}$ and HOMO energies is larger than the contribution of carbonyl group for the $E_{pc}^{(-)}$ and LUMO energies.

Unidirectional Photo-induced Charge Separation and Thermal Charge Recombination of Cofacially Aligned Donor-Acceptor System Probed by Ultrafast Visible-Pump/Mid-IR-Probe Spectroscopy

  • Kim, Hyeong-Mook;Park, Jaeheung;Noh, Hee Chang;Lim, Manho;Chung, Young Keun;Kang, Youn K.
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.587-596
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    • 2014
  • A new ${\pi}$-stacked donor-acceptor (D-A) system, [Ru(1-([2,2'-bipyridine]-6-yl-methyl)-3-(2-cyclohexa-2',5'-diene-1,4-dionyl)-1H-imidazole)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (ImQ_T), has been synthesized and characterized. Similar to its precedent, [Ru(6-(2-cyclohexa-2',5'-diene-1,4-dione)-2,2':6',2"-terpyridine)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (TQ_T), this system has a cofacial alignment of terpyridine (tpy) ligand and quinonyl (Q) group, which facilitates an electron transfer through ${\pi}$-stacked manifold. Despite the presence of lowest-energy charge transfer transition from the Ru-based-HOMO-to-Q-based-LUMO (MQCT) predicted by theoretical calculations by using time-dependent density functional theory (TD-DFT), the experimental steady-state absorption spectrum does not exhibit such a band. The selective excitation to the Ru-based occupied orbitals-to-tpy-based virtual orbital MLCT state was thus possible, from which charge separation (CS) reaction occurred. The photo-induced CS and thermal charge recombination (CR) reactions were probed by using ultrafast visible-pump/mid-IR-probe (TrIR) spectroscopic method. Analysis of decay kinetics of Q and $Q^-$ state CO stretching modes as well as aromatic C=C stretching mode of tpy ligand gave time constants of <1 ps for CS, 1-3 ps for CR, and 10-20 ps for vibrational cooling processes. The electron transfer pathway was revealed to be Ru-tpy-Q rather than Ru-bpy-imidazol-Q.

Analysis of BNNT(Boron Nitride Nano Tube) synthesis by using Ar/N2/H2 60KW RF ICP plasma in the difference of working pressure and H2 flow rate

  • Cho, I Hyun;Yoo, Hee Il;Kim, Ho Seok;Moon, Se Youn;Cho, Hyun Jin;Kim, Myung Jong
    • Proceedings of the Korean Vacuum Society Conference
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    • 2016.02a
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    • pp.179-179
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    • 2016
  • A radio-frequency (RF) Inductively Coupled Plasma (ICP) torch system was used for boron-nitride nano-tube (BNNT) synthesis. Because of electrodeless plasma generation, no electrode pollution and effective heating transfer during nano-material synthesis can be realized. For stable plasma generation, argon and nitrogen gases were injected with 60 kW grid power in the difference pressure from 200 Torr to 630 Torr. Varying hydrogen gas flow rate from 0 to 20 slpm, the electrical and optical plasma properties were investigated. Through the spectroscopic analysis of atomic argon line, hydrogen line and nitrogen molecular band, we investigated the plasma electron excitation temperature, gas temperature and electron density. Based on the plasma characterization, we performed the synthesis of BNNT by inserting 0.5~1 um hexagonal-boron nitride (h-BN) powder into the plasma. We analysis the structure characterization of BNNT by SEM (Scanning Electron Microscopy) and TEM (Transmission Electron Microscopy), also grasp the ingredient of BNNT by EELS (Electron Energy Loss Spectroscopy) and Raman spectroscopy. We treated bundles of BNNT with the atmospheric pressure plasma, so that we grow the surface morphology in the water attachment of BNNT. We reduce the advancing contact angle to purity bundles of BNNT.

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Estimation of Energetic and Charge Transfer Properties of Iridium(III) Bis(2-phenylpyridinato-N,C2')acetylacetonate by Electrochemical Methods

  • Cha, Joeun;Ko, Eun-Song;Shin, Ik-Soo
    • Journal of Electrochemical Science and Technology
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    • v.8 no.2
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    • pp.96-100
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    • 2017
  • Iridium(III) bis(2-phenylpyridinato-$N,C^{2^{\prime}}$)acetylacetonate ($(ppy)_2Ir(acac)$), a green dopant used in organic light-emitting devices (OLEDs), was subjected to electrochemical characterization to estimate its formal oxidation potential ($E^{o^{\prime}}$), HOMO energy level ($E_{HOMO}$), electron transfer rate constant ($k^{o^{\prime}}$), and diffusion coefficient ($D_o$). The employed combination of voltammetric methods, i.e., cyclic voltammetry (CV), chronocoulometry (CC), and the Nicholson method, provided meaningful insights into the electron transfer kinetics of $(ppy)_2Ir(acac)$, allowing the determination of $k^{o^{\prime}}$ and $D_o$. The quasi-reversible oxidation of $(ppy)_2Ir(acac)$ furnished information on $E^{o^{\prime}}$ and $E_{HOMO}$, allowing the latter parameter to be easily estimated by electrochemical methods without relying on expensive and complex ultraviolet photoemission spectroscopic (UPS) measurements.