• Bulletin of the Korean Chemical Society
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• 제34권8호
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• pp.2271-2275
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• 2013

We report on the photoelectrochemical properties of partially reduced mesoporous titania thin films. The fabrication is achieved by synthesizing mesoporous titania thin films through the self-assembly of a titania precursor and a block copolymer, followed by aging and calcination, and heat-treatment under a $H_2$ (1 torr) environment. Depending on the temperature used for the reaction with $H_2$, the degree of the reduction (generation of oxygen vacancies) of the titania is controlled. The oxygen vacancies induce visible light absorption, and decrease of resistance while the mesoporosity is practically unaltered. The photoelectrochemical activity data on these films, by measuring their photocurrent-potential behavior in 1 M NaOH electrolyte under AM 1.5G 100 mW $cm^{-2}$ illumination, show that the three effects of the oxygen vacancies contribute to the enhancement of the photoelectrochemical properties of the mesoporous titania thin films. The results show that these oxygen deficient $TiO_2$ mesoporous thin films hold great promise for a solar hydrogen generation. Suggestions for the materials design for improved photoelectrochemical properties are made.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2012년도 춘계학술발표대회
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• pp.70.1-70.1
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• 2012

In-situ X-ray photoelectron spectroscopy (XPS) and infrared (IR) spectroscopy studies of SOFC cathode materials will be discussed in this presentation. The mixed conducting perovskites (ABO3) containing rare and alkaline earth metals on the A-site and a transition metal on the B-site are commonly used as cathodes for solid oxide fuel cells (SOFC). However, the details of the oxygen reduction reaction are still not clearly understood. The information about the type of adsorbed oxygen species and their concentration is important for a mechanistic understanding of the oxygen incorporation into these cathode materials. XPS has been widely used for the analysis of adsorbed species and surface structure. However, the conventional XPS experiments have the severe drawback to operate at room temperature and with the sample under ultrahigh vacuum (UHV) conditions, which is far from the relevant conditions of SOFC operation. The disadvantages of conventional XPS can be overcome to a large extent with a "high pressure" XPS setup installed at the BESSY II synchrotron. It allows sample depth profiling over 2 nm without sputtering by variation of the excitation energy, and most importantly measurements under a residual gas pressure in the mbar range. It is also well known that the catalytic activity for the oxygen reduction is very sensitive to their electrical conductivity and oxygen nonstoichiometry. Although the electrical conductivity of perovskite oxides has been intensively studied as a function of temperature or oxygen partial pressure (Po2), in-situ measurements of the conductivity of these materials in contact with the electrolyte as a SOFC configuration have little been reported. In order to measure the in-plane conductivity of an electrode film on the electrolyte, a substrate with high resistance is required for excluding the leakage current of the substrate. It is also hardly possible to measure the conductivity of cracked thin film by electrical methods. In this study, we report the electrical conductivity of perovskite $La_{0.6}Sr_{0.4}CoO_{3-{\delta}}$ (LSC) thin films on yttria-stabilized zirconia (YSZ) electrolyte quantitatively obtained by in-situ IR spectroscopy. This method enables a reliable measurement of the electronic conductivity of the electrodes as part of the SOFC configuration regardless of leakage current to the substrate and cracks in the film.

• 한국세라믹학회지
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• 제53권3호
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• pp.306-311
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• 2016

Li-air batteries have received much attention due to their superior theoretical energy density. However, their sluggish kinetics on the cathode side is considered the main barrier to high performance. The rational design of electrode catalysts with high activity is therefore an important challenge. To solve this issue, we performed density functional theory (DFT) calculations to analyze the adsorption behavior of the $LiO_2$ molecule, which is considered to be a key intermediate in both the Li-oxygen reduction reaction (ORR) and the evolution reaction (OER). Specifically, to use the activity descriptor approach, the $LiO_2$ adsorption energy, which has previously been demonstrated to be a reliable descriptor of the cathode reaction in Li-air batteries, was calculated on $LaB_{1-x}B^{\prime}_xO_3$(001) (B, B' = Mn, Fe, Co, and Ni, x = 0.0, 0.5). Our fast screening results showed that $LaMnO_3$, $LaMn_{0.5}Fe_{0.5}O_3$, or $LaFeO_3$ would be good candidate catalysts. We believe that our results will provide a way to more efficiently develop new cathode materials for Li-air batteries.

• 한국세라믹학회지
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• 제56권5호
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• pp.497-505
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• 2019

Lanthanum-based transition metal cations containing perovskites have emerged as potential catalysts for the intermediate-temperature (600-800℃) oxygen reduction reaction (ORR). Here, we report a facile acetylacetone-assisted combustion route for the synthesis of nanostructured La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF6428) cathodes for intermediate-temperature solid-oxide fuel cells (IT-SOFCs). The as-prepared powder was analyzed by thermogravimetry analysis-differential scanning calorimetry. The powder calcined at 800℃ was characterized by X-ray diffraction, scanning electrode microscopy, energy dispersive X-ray spectroscopy, and Brunauer-Emmett-Teller surface area measurements. It was found that the porosity of the air electrode significantly increased by utilizing the nanostructured LSCF6428 instead of commercial powder. The performance of a single cell fabricated with the nanostructured LSCF6428 cathode increased by 112%, from 0.4 to 0.85 W cm^-2, at 700℃. Electrochemical impedance spectroscopy showed a considerable reduction in the area-specific resistance and activation energy from 133.5 to 61.5 kJ/mol, resulting in enhanced electrocatalytic activity toward ORR and overall cell performance.

• 한국대기환경학회지
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• 제6권1호
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• pp.31-42
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• 1990

In order to suggest an efficient catalyst systems for NOx reduction of flue gases from industrial boilers, $TiO_2$ supported $WO_3-V_2O_5, V_2O_5$ and $WS_2$ catalysts were tested for the performances of NOx reduction at high reactin temperature range (250-500$^\circ$C) using a simulated flue gas system. It was found that while the proposed $WO_3/TiO_2$ and $WO_3-V_2O_5/TiO_2$ catalysts showed a significant high NOx reduction efficiency at about 350-400$^\circ$C, the conventional commercial catalyst of $V_2O_5/TiO_2$ showed a significant drop in NOx reduction efficiency due to the excessive $NH_3$ oxidation. From the measurement of surface acidities of those catalysts, it was found that the acidity are well correlated with the activities of NOx reduction. The reason of high activity of $WO_3$ series catalysts at high reaction temperature seems due to the low value of surface excess oxygen compared with that of $V_2O_5/TiO_2$ seems equivalent to the acid site of that catalyst.

• 청정기술
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• 제17권3호
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• pp.225-230
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• 2011

다양한 귀금속 촉매를 이용한 hydrocarbon selective catalytic reduction 반응특성을 조사하였다. 가장 우수한 활성금속은 Pt, 지지체는 활성금속과 지지체간 강한 상호작용에 의하여 $CeO_2$, $TiO_2$였으며, NOx 전환율은 약 55%를 나타내었다. 활성금속으로서 Pd, Rh, Ag 촉매들은 20% 미만의 전환율을 보였으며, 지지체로서 $SiO_2$, $ZrO_2$ 또한 다른 지지체들보다 저조한 활성을 나타내었다. 조업조건에 따른 촉매의 성능을 조사하기 위하여 환원제의 종류, 양, 산소농도, 공간속도에 따른 실험을 수행하였다. 환원제로서 메탄이 프로판보다 우수함을 확인하였고, 메탄/질소 산화물 비가 증가할수록 성능이 우수하였으며, 산소농도가 증가할수록, 그리고 공간속도가 감소할수록 촉매의 성능은 증가함을 확인할 수 있었다.

• 공업화학
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• 제30권4호
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• pp.493-498
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• 2019

수소연료전지의 백금 촉매층은 높은 활성을 가지고 있어야 하며, 물과 산소의 원활한 물질전달을 위하여 얇은 두께를 유지해야 한다. 이를 위해 수열 합성 기반의 높은 백금 함량의 담지 촉매 합성법이 보고되어 왔지만, 반응과정에서의 입자 성장 거동 및 속도에 대한 접근은 상대적으로 희박하다. 본 연구에서는 환원과정이 완료된 현탁액을 교반하면서 백금 결정의 성장을 시간별로 관찰하였고 이의 전기화학적 활성을 평가하였다. 초반 교반과정 단계의 단지 수 시간에서 백금 콜로이드가 탄소 담지 백금 촉매에 붙어 백금 결정을 성장시키는 것을 확인하였다. 그 이후에는 새로운 핵성장 반응으로 크기가 작은 콜로이드가 형성되지만, 백금 결정 성장에는 참여하지 않는 것을 확인하였다. 따라서 6 h만 교반과정을 겪은 탄소 담지 백금 촉매도 산소환원반응에 대해 우수한 성능을 가지고 있음을 확인하였다.

• Journal of Electrochemical Science and Technology
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• 제5권2호
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• pp.49-52
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• 2014

Graphene nanosheets (GNS), nitrogen-doped graphene nanosheets (N-GNS), and sulfur-doped graphene nanosheets (S-GNS) were successfully synthesized, and their catalytic effects on the oxygen reduction reaction (ORR) in $Li-O_2$ batteries were compared. The S-GNS electrode exhibited the highest ORR catalytic activity, resulting in enhanced discharge capacity and power capability. We attributed the enhanced ORR catalytic activity to the increased defect sites on graphene.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2011년도 추계학술대회 초록집
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• pp.93-93
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• 2011

Nanostructures consisting of $TiO_2$ particles as a core and carbon as a shell ($TiO_2$@C) were prepared by heat treatment of $TiO_2$ nanoparticles at high temperature in a methane atmosphere. X-ray diffraction and transmission electron microscopy showed that a carbon shell layer was formed well. These structures were used as supports for platinum nanoparticles and the hybrid particles exhibit improved catalytic activity and stability toward ORR compared to Pt on a carbon black (Vulcan XC-72R). It is likely that enhanced catalytic properties of the Pt on $TiO_2$@C could be due to the stability of the core-shell support in comparison with carbon black support.

• 에너지공학
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• 제23권3호
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• pp.157-162
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• 2014

해당 연구에서는 수정된 폴리올법을 이용하여 합성한 카본블랙 탄소지지체의 Pt촉매의 전기적, 전기화학적 특성을 평가하였다. 또한 Polyol_Pt/C 촉매는 고분자전해질연료전지의 공기극에 적용하여 산소환원반응성을 측정하였다. 산소환원반응성과 고분자전해질연료전지 성능평가를 통해 상용 Pt/C (JM_Pt/C)촉매와 비교하여 전기화학적인 촉매성능을 비교하였다. 촉매의 활성표면적을 구하기 위해 순환전압전류주사법을 이용하였고, 산소환원반응성을 측정하기 위해 회전원판전극으로 선형주사전류법을 이용하였다. 또한 고분자전해질연료전지 완전지 성능 측정을 진행하였다. 그 결과 Polyol_Pt/C 촉매의 활성표면적 ($196m^2g^{-1}$)은 JM_Pt/C 촉매의 그 값 ($183m^2g^{-1}$) 보다 우수하였다. 촉매들의 산소환원반응성에 경우에도 Polyol_Pt/C 촉매는 JM_Pt/C 촉매보다 우수한 반파장전위 및 한계전류밀도를 나타내었다. 또한 완전지 평가시, MEA 공기극을 위한 Polyol_Pt/C 촉매 담지량을 기존의 0.4에서 0.15로 줄였을 때, 성능저하가 적게 나타났고, 300시간의 장기간 성능 평가에서도 연료전지 성능이 거의 일정하게 유지되었다. 이를 토대로 수정된 폴리올법에 의해 합성된 Polyol_Pt/C 촉매는 경제적인 이용 및 우수한 내구성을 가지고 있음을 밝혀내었다.