• 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.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2016년도 제50회 동계 정기학술대회 초록집
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• pp.394-394
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• 2016

The oxygen reduction reaction (ORR) in a polymer electrolyte membrane (PEM) fuel cell requires the use of Pt-based catalysts. Due to the high cost and low abundance of Pt, many researchers have been studied to reduce the use of Pt while to enhance the catalytic performance of Pt. One of the promising strategies is the deposition of Pt as ultrathin skins of only a few atomic layers on nanoscale substrates made of another metal. This presentation will discuss the conformal deposition of Pt as uniform, ultrathin shells on Pd nanocrystals. By optimizing the catalytic behavior of Pt-based nanocrystals, we obtained the greatly enhanced ORR activity and durability.

• Journal of Electrochemical Science and Technology
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• 제12권1호
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• pp.137-145
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• 2021

Among the non-precious metal catalysts, iron-nitrogen doped carbon (Fe-N/C) catalysts have been recognized as the most promising candidates for an alternative to Pt-based catalysts for the oxygen reduction reaction (ORR) under alkaline and acidic conditions. In this study, the nano replication method using mesoporous silica, which features tunable primary particle sizes and shape, is employed to prepare the mesoporous Fe-N/C catalysts with different shapes. Platelet SBA-15, irregular KIT-6, and spherical silica particle (SSP) were selected as a template to generate three different kinds of shapes of the mesoporous Fe-N/C catalyst. Physicochemical properties of mesoporous Fe-N/C catalysts are characterized by using small-angle X-ray diffraction, nitrogen adsorption-desorption isotherms, and scanning electron microscopy images. According to the electrochemical evaluation, there is no morphological preference of mesoporous Fe-N/C catalysts toward the ORR activity with half-cell configuration under alkaline electrolyte. By implementing X-ray photoelectron spectroscopy analysis of Fe and N atoms in the mesoporous Fe-N/C catalysts, it is possible to verify that the activity towards ORR highly depends on the portions of "Fe-N" species in the catalysts regardless of the shape of catalysts. It was suggested that active site distribution in the Fe-N/C is one important factor towards ORR activity.

• Korean Chemical Engineering Research
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• 제60권1호
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• pp.151-158
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• 2022

고가의 귀금속 촉매는 고분자 전해질 연료전지의 상업화에 걸림돌로 인식되어 저가의 비귀금속 촉매 연구가 활발하다. 본 연구에서는 Fe-N-C 촉매를 킬레이팅이 가능한 4가지 다른 질소 전구체 N,N,N',N'-detramethylethylenediamine(TMEDA), 1,2-ethylenediamine (EDA), m-dicyanobenzene (DCB), dicyandiamide (DCDA)를 이용하여 700, 800, 900, 1000 ℃에서 합성하였다. 촉매의 물리적 특성은 주사전자현미경, X선 회절분석기, 자동원소분석기를 이용하여 분석하였다. 이를 통해 촉매 표면 형태 및 원소의 분산도와 에너지 분산형 X-선 분광을 적용하여 Fe의 함량을 확인하였다. 또한 비금속 원소의 함량과 Fe의 담지 여부 등을 확인하였다. 전기화학적 특성은 순환 전압전류법과 선형주사전위법을 통해 촉매의 전기화학적 산소 환원에 대한 활성과 전자전달수 등을 분석하였다. 결과에 따르면 질소 전구체로 EDA를 사용하여 800 ℃의 소성온도에서 합성한 촉매가 가장 높은 산소 환원 활성을 보였다. 이 연구 결과는 고가의 귀금속을 대체하기 위한 노력에 도움이 될 것으로 예상된다.

• 전기화학회지
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• 제16권1호
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• pp.52-58
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• 2013

고분자 전해질 연료전지(Polymer Electrolyte Membrane Fuel Cell, PEMFC) 상용화를 위해 해결해야 할 과제 중의 하나인 가격 저감을 이루기 위한 방법으로 백금 촉매를 대신할 비귀금속(non-precious metal) 촉매 제조에 관한 연구를 수행하였다. 비귀금속 촉매의 합성은 산소환원반응(oxygen reduction reaction, ORR)의 활성점으로 알려져 있는 코발트-질소(Co-N) 결합을 형성하기 위해 질소를 포함하는 폴리아닐린(PANI)과 코발트염(Co precursor), 그리고 카본 블랙(C)을 일정한 비율대로 혼합한 후 특별한 열처리 과정 없이 단순한 화학적 환원법에 제조되었다. 제조된 Co-PANI-C 복합 촉매의 구조 분석을 위해 X-선 회절분석(X-ray diffraction, XRD)과 열중량분석(thermogravimetric analysis, TGA)을 실시하였고, ORR에 대한 활성을 평가하기 위해 rotating disk electrode(RDE) 및 rotating ring disk electrode(RRDE) 측정을 수행하였다. 그 결과 Co-PANI-C 복합 촉매는 ORR반응에 대한 개시 전압은 백금 촉매보다 60 mV 밖에 낮지 않은 값을 보였지만, 반응에 의해 발생되는 환원 전류는 여전히 백금 촉매보다 낮은 값을 보였다. 이 밖에도 전극 회전 속도에 따른 ORR 특성 변화, 전압 사이클 회수에 따른 내구성 변화, 연료전지 적용 시 성능 변화에 대해 논의할 것이다.

• 한국수소및신에너지학회논문집
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• 제32권1호
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• pp.41-52
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• 2021

NiO and Co3O4-doped porous La(CoNi)O3 perovskite oxides were prepared from excess Ni addition by a hydrothermal method using porous silica template, and characterized as bifunctional catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) for Zn-air rechargeable batteries in alkaline solution. Excess Ni induced to form NiO and Co3O4 in La(CoNi)O3 particles. The NiO and Co3O4-doped porous La(CoNi)O3 showed high specific surface area, up to nine times of conventionally synthesized perovskite oxide, and abundant pore volume with similar structure. Extra added Ni was partially substituted for Co as B site of ABO3 perovskite structure and formed to NiO and Co3O4 which was highly dispersed in particles. Excess Ni in La(CoNi)O3 catalysts increased OER performance (259 mA/㎠ at 2.4 V) in alkaline solution, although the activities (211 mA/㎠ at 0.5 V) for ORR were not changed with the content of excess Ni. La(CoNi)O3 with excess Ni showed very stable cyclability and low capacity fading rate (0.38 & 0.07 ㎶/hour for ORR & OER) until 300 hours (~70 cycles) but more excess content of Ni in La(CoNi)O3 gave negative effect to cyclability.

• 한국수소및신에너지학회논문집
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• 제29권5호
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• pp.450-457
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• 2018

To design the practical core-shell electrocatalysts, combination of core and shell materials is important to meet catalytic activity and durability target. In general, Pd is considered as a good core material due to its best activity caused by strain/ligand effect. Preparing Pd nanoparticles can be a starting point in fabricating core-shell type electrocatalysts, much simplified Pd preparing process is suggested by using carbon monoxide (CO) as a reducing agent and/or capping agent. The solvent composition and reaction temperature can control to nanosheet, tetrahedron, and sphere without using additional stabilizer. Among them, Pd nanosheet which has mainly (111) plane showed about 3 times higher electrocatalytic activity for oxygen reduction reaction (ORR) to the spherical Pd nanoparticles. The enhanced ORR activity of Pd nanosheets can be attributed to the exposure of Pd (111) surface and the high electrochemical surface area. Therefore, we demonstrated that the shape of Pd nanomaterials is easily controlled via a facile reduction method using CO, and (111) plane-oriented Pd nanosheets can be a promising ORR catalysts and core material for polymer electrolyte fuel cells (PEFCs).

• 한국재료학회지
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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.

• 한국수소및신에너지학회논문집
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• 제25권4호
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• pp.378-385
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• 2014

In this research, we investigate electrical performance and electrochemical properties of graphene supported Pt (Pt/G) and PtM (M = Ni and Y) alloy catalysts (PtM/Gs) that are synthesized by modified polyol method. With the PtM/Gs that are adopted for oxygen reduction reaction (ORR) as cathode of proton exchange membrane fuel cells (PEMFCs), their catalytic activity and ORR performance and electrical performance are estimated and compared with one another. Their particle size, particle distribution and electrochemically active surface (EAS) area are measured by TEM and cyclic voltammetry (CV), respectively. On the other hand, regarding ORR activity and electrical performance of the catalysts, (i) linear sweeping voltammetry by rotating disk electrode and rotating ring-disk electrode and (ii) PEMFC single cell tests are used. The TEM and CV measurements demonstrate particle size and EAS of PtM/Gs are compatible with those of Pt/G. In case of PtNi/G, its half-wave potential, kinetic current density, transferred electron number per oxygen molecule and $H_2O_2$ production % are excellent. Based on data obtained by half-cell test, when PEMFC singlecell tests are carried out, current density measured at 0.6V and maximum power density of the PEMFC single cell employing PtNi/G are better than those employing Pt/G. Conclusively, PtNi/Gs synthesized by modified polyol shows better ORR catalytic activity and PEMFC performance than other catalysts.

• 한국표면공학회:학술대회논문집
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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 (${\approx}4$).