• Journal of Electrochemical Science and Technology
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• 제7권4호
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• pp.298-305
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• 2016

The development of non-precious metal based electrocatalysts is highly desired for the oxygen reduction reaction (ORR) as alternates to noble metal based ORR electrocatalysts. Herein, we report mononulcear copper(II) complex $[CuLbpy]ClO_4$ (L=4-[(2-hydroxyphenylimino)methyl]benzoic acid) containing poly(allylamine.HCl) polymer (PAlACuLbpy) as an electrocatalyst for oxygen reduction reaction (ORR). PAlACuLbpy was mixed with poly(acrylic acid) and tetraethylortho silicate to prepare a composite and then deposited on the screen printed electrode surface. The modified electrode (PAlACuLbpy/PCE) is highly stable and showed a quasi-reversible redox behavior with $E_{1/2}=-0.2V$ vs. Ag/AgCl(3 M KCl) in 0.1 M phosphate buffer at pH 7 under argon atmosphere. PAlACuLbpy/PCE exhibited a remarkable ORR activity with an onset potential of -0.1 V vs Ag/AgCl in 0.1 M PB (pH 7) in the presence of oxygen. The kinetics for ORR was studied by rotating disk voltammetry in neutral aqueous medium and the results indicated that the number of electrons involving in the ORR is four and the conversion products are water and hydrogen peroxide.

• Journal of the Korean Electrochemical Society
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• 제15권1호
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• pp.12-18
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• 2012

The prohibitively high cost of Pt catalyst might be the biggest barrier for the commercialization of proton exchange membrane fuel cells (PEMFC) of which wide application is expected. Worldwide research efforts for the development of alternative to Pt oxygen reduction reaction (ORR) catalyst are made recently. One of the important considerations in the catalyst development is durability issue as well as economic aspect. From this point of view, platinum group metals (PGM) except Pt can be a candidate for replacing Pt catalyst because the material properties and the catalytic activity of PGM are expected to be similar to Pt. In contrast to Ir, Rh and Os to which not so much attention has been paid as an ORR catalyst, Pd that is most similar to Pt in terms of material properties and catalytic activity and Ru that is in the form of chalcogenide have been studied intensively. Activity comparison between non-Pt and Pt oxygen reduction catalysts by half cell test using RDE (rotating disk electrode) or PEMFC MEA (membrane electrode assembly) operation indicates that Pd-based catalysts show the most similar activity to Pt. In this paper we analyze the composition of PGM ORR catalyst in literature to promote the development of non-Pt ORR catalyst.

• Carbon letters
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• 제17권1호
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• pp.53-64
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• 2016

Nitrogen (N)-doped ordered mesoporous carbons (OMCs) with a dual transition metal system were synthesized as non-Pt catalysts for the ORR. The highly nitrogen doped OMCs were prepared by the precursor of ionic liquid (3-methyl-1-butylpyridine dicyanamide) for N/C species and a mesoporous silica template for the physical structure. Mostly, N-doped carbons are promoted by a single transition metal to improve catalytic activity for ORR in PEMFCs. In this study, our N-doped mesoporous carbons were promoted by the dual transition metals of iron and cobalt (Fe, Co), which were incorporated into the N-doped carbons lattice by subsequently heat treatments. All the prepared carbons were characterized by via transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). To evaluate the activities of synthesized doped carbons, linear sweep was recorded in an acidic solution to compare the ORR catalytic activities values for the use in the PEMFC system. The dual transition metal promotion improved the ORR activity compared with the single transition metal promotion, due to the increase in the quaternary nitrogen species from the structural change by the dual metals. The effect of different ratio of the dual metals into the N doped carbon were examined to evaluate the activities of the oxygen reduction reaction.

• Journal of the Korean Electrochemical Society
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• 제15권2호
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• pp.90-94
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• 2012

We report nanostructure electrodes with $TiO_2$ as a core and carbon as a shell ($TiO_2$@C) for oxygen reduction in alkaline solution. The structure of core-shell electrodes is characterized by transmission electron microscopy, Raman spectroscopy, X-ray diffraction method, and X-ray photoelectron microscopy. The electrochemical properties of the $TiO_2$@C electrodes are characterized using a potentiostat and compared with those of carbon supported Pt catalyst. In particular, the core-shell electrode with dominant pyridinic-N component exhibits an imporved electrocatalytic activity for oxygen reduction reaction in alkaline solution.

• Environmental Sciences Bulletin of The Korean Environmental Sciences Society
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• 제4권4호
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• pp.201-208
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• 2000

The reduction of NO by hydrocarbons was investigated over Cu/Al$_2$O$_3$catalysts using a stainless steel flow reactor under highly oxidising diesel exhaust conditions(up to 15%). Three different Cu loadings(1,5 and 10wt.%) on an $Al_2$O$_3$support were prepared and characterized using spectroscopic techniques. The catalytic activity tests show that different Cu loadings as well as temperature, oxygen, and hydrocarbon concentration levels significantly influence the NO reduction. Increasing Cu loadings up to 5 and 10wt.% decreases the catalytic activities for NO reduction due to the formation of a bulk crystalline CuO phase, as observed from XRD and SEM images. In particular, the visualization of the copper dispersion on the surface using the SEM-BEI technique provides information on the extent of copper saturation, particle size, and the effects on NO reduction. However, the lower Cu loading(1 wt.%) increases the catalytic activity with a temperature window of 720-810K, thereby favoring the formation of well dispersed isolated Cu species, e.g. Cu(sup)2+ ions, which is related to selective NO reduction. The effects of other reaction parameters, such as oxygen, the hydrocarbon level and type, and byproduct emissions are further discussed.

• Journal of Electrochemical Science and Technology
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• 제7권1호
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• pp.27-32
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• 2016

Although the time dependences of the electrocatalytic activities of Pt and Pd nanoparticles during electrochemical operations have been widely studied, the time dependences under nonpolarized conditions have never been investigated in depth. This study reports the changes in the electrocatalytic activities of Pt and Pd nanoparticles with aging in air and in solution. Pt (or Pd) nanoparticle-modified electrodes are obtained by adsorbing citrate-stabilized Pt (or Pd) nanoparticles on amine-modified indium-tin oxide (ITO) electrodes, or by electrodeposition of Pt (or Pd) nanoparticles on ITO electrodes. The electrocatalytic activities of freshly prepared Pt and Pd nanoparticles in the oxygen reduction reaction slowly decrease with aging. The electrocatalytic activities decrease more slowly in solution than in air. An increase in surface contamination may cause electrocatalytic deactivation during aging. The electrocatalytic activities of long-aged Pt (or Pd) nanoparticles are significantly enhanced and recovered by NaBH₄ treatment.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 한국표면공학회 2018년도 춘계학술대회 논문집
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• pp.62-62
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• 2018

Pt is still considered as one of the most active electrocatalysts for ORR in alkaline fuel cells. However, the high cost and scarcity of Pt hamper the widespread commercialization of fuel cells. As a strong candidate for the replacement of Pt catalyst, silver (Ag) has been extensively studied due to its high activity, abundance, and low cost. Ag is more stable than Pt in the pH range of 8~14 as the equilibrium potential of Ag/Ag+ being ${\approx}200mV$ higher than that of Pt/PtO. However, Ag is the overall catalytic activity of Ag for oxygen reduction reaction(ORR) is still not comparable to Pt catalyst since the surface Ag atoms are approximately 10 times less active than Pt atoms. Therefore, further enhancement in the ORR activity of Ag catalysts is necessary to be competitive with current cutting-edge Pt-based catalysts. We demonstrate the architectural design of Ag catalysts, synthesized using plasma discharge in liquid phase, for enhanced ORR kinetics in alkaline media. An attractive feature of this work is that the plasma status controlled via electric-field could form the Ag nanowires or dendrites without any chemical agents. The plasma reactor was made of a Teflon vessel with an inner diameter of 80 mm and a height of 80 mm, where a pair of tungsten(W) electrodes with a diameter of 2 mm was placed horizontally. The stock solutions were made by dissolving the 5-mM AgNO3 in DI water. For the synthesis of Agnanowires, the electricfield of 3.6kVcm-1 in a 200-ml AgNO3 aqueous solution was applied across the electrodes using a bipolar pulsed power supply(Kurita, Seisakusyo Co. Ltd). The repetition rate and pulse width were fixed at 30kHz and 2.0 us, respectively. The plasma discharge was carried out for a fixed reaction time of 60 min. In case of Ag nanodendrites, the electric field of 32kVcm-1 in a 200-ml AgNO3 aqueous solution was applied and other conditions were identical to the plasma discharge in water in terms of electrode configuration, repetition rate and discharge time. Using SEM and STEM, morphology of Ag nanowires and dendrites were investigated. With 3.6 kV/cm, Ag nanowire was obtained, while Ag dendrite was constructed with 32 kV/cm. The average diameter and legth of Ag nanowireses were 50 nm and 3.5 um, and thoes values of Ag dendrites were 40 nm and 3.0 um. As a results of XPS analysis, the surface defects in the Ag nanowires facilitated O2 incorporation into the surface region via the interaction between the oxygen and the electron cloud of the adjacent Ag atoms. The catalytic activity of Ag for oxygen reduction reaction(ORR) showed that the catalytic ORR activity of Ag nanowires are much better than Ag nanodendrites, and electron transfer number of Ag nanowires is similar to that of Pt (${\approx}4$).

• Applied Chemistry for Engineering
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• 제31권5호
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• pp.560-567
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• 2020

In this study, we investigated that the effect of alkali metals [Na(Sodium) and K(Potassium)], known as representative deactivating substances among exhaust gases of various industrial processes, on the NH₃-SCR (selective catalytic reduction) reaction of V/W/TiO₂ catalysts. NO, NH₃-TPD (temperature programmed desorption), DRIFT (diffuse reflectance infrared fourier transform spectroscopy analysis), and H₂-TPR analysis were performed to determine the cause of the decrease in activity. As a result, each alkali metal acts as a catalyst poisoning, reducing the amount of NH₃ adsorption, and Na and K reduce the SCR reaction by reducing the L and B acid points that contribute to the reaction activity of the catalyst. Through the H₂-TPR analysis, the alkali metal is considered to be the cause of the decrease in activity because the reduction temperature rises to a high temperature by affecting the reduction temperature of V-O-V (bridge oxygen bond) and V=O (terminal bond).

• Korean Journal of Materials Research
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• 제21권3호
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• pp.180-185
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• 2011

This study is aimed to increase the activity of cathodic catalysts for PEMFCs(Polymer Electrolyte Membrane Fuel Cells). we investigated the temperature effect of 20wt% Pt/C catalysts at five different temperatures. The catalysts were synthesized by using chemical reduction method. Before adding the formaldehyde as reducing agent, process was undergone for 2 hours at the room temperature (RT), $40^{\circ}C$, $60^{\circ}C$, $80^{\circ}C$ and $100^{\circ}C$, respectively. The performances of synthesize catalysts are compared. The electrochemical oxygen reduction reaction (ORR) was studied on 20wt% Pt/C catalysts by using a glassy carbon electrode through cyclic voltammetric curves (CV) in a 1M H2SO4 solution. The ORR specific activities of 20wt% Pt/C catalysts increased to give a relative ORR catalytic activity ordering of $80^{\circ}C$ > $100^{\circ}C$ > $60^{\circ}C$ > $40^{\circ}C$ > RT. Electrochemical active surface area (EAS) was calculated with cyclic voltammetry analysis. Prepared Pt/C (at $80^{\circ}C$, $100^{\circ}C$) catalysts has higher ESA than other catalysts. Physical characterization was made by using X-ray diffraction (XRD) and transmission electron microscope (TEM). The TEM images of the carbon supported platinum electrocatalysts ($80^{\circ}C$, $100^{\circ}C$) showed homogenous particle distribution with particle size of about 2~3.5 nm. We found that a higher reaction temperature resulted in more uniform particle distribution than lower reaction temperature and then the XRD results showed that the crystalline structure of the synthesized catalysts are seen FCC structure.

• Environmental Engineering Research
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• 제13권4호
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• pp.210-215
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• 2008

The present study investigates the effect of oxidation-reduction potential (ORP) and organic compounds on specific anaerobic ammonium oxidation activity (SAA) using batch experiments. The batch tests were based on the measurement of nitrogen gas production. The relationship between ORP and dissolved oxygen (DO) concentration was found to be ORP (mV) = 160.38 + 68 log [$O_2$], where [$O_2$] is the DO concentration in mg/L. The linear relationship obtained between ORP and SAA ($R^2$ = 0.99) clearly demonstrated that ORP can be employed as an operational parameter in the Anammox process. At ORP value of -110 mV, the SAA was $0.272{\pm}0.03\;g\;N_2-N\;(g\;VSS)^{-1}\;d^{-1}$. The investigation also revealed inhibitory effect of glucose on the SAA while acetate concentration up to 640 mg COD/L (corresponding to 10 mM) had stimulating effect on the SAA. However, acetate concentration beyond 640 mg COD/L had inhibitory effect on the Anammox activity. The results indicated that nitrogen rich wastewaters containing low level organic matter could be better treated by Anammox microorganisms in real-world conditions after some acidification process.