• 한국수소및신에너지학회논문집
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• 제25권2호
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• pp.105-113
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• 2014

Performance tests on $Ni/Ce-ZrO_2/Al_2O_3$ catalysts with additives (MgO, $La_2O_3$) were investigated in the combined reforming processes (SCR, ATR, TRM) in order to produce hydrogen and carbon monoxide (it is called "syngas".). The catalyst characterization was conducted using the BET surface analyzer, X-ray diffraction (XRD), SEM, TPR and TGA. The combined reforming process was developed to adjust the syngas ratio depending on the synthetic fuel (methanol, DME and GTL) manufacturing processes. Ni-based catalysts supported on alumina has been generally recommended as a combined reforming reaction catalyst. It was found that both free NiO and complexed NiO species were responsible for the catalytic activity in the combined reforming of methane conversion, and the $Ce-ZrO_2$ binary support employed had improved the oxygen storage capacity and thermal stability. The additives, MgO and $La_2O_3$, also seemed to play an important role to prevent the formation of the carbon deposition over the catalysts. The experimental results were compared with the equilibrium data using a commercial simulation tool (PRO/II).

• 공업화학
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• 제4권2호
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• pp.308-317
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• 1993

본 연구는 Mo-V-W 다성분 혼합산화물 촉매상에서 아크로레인의 선택산화에 의한 아크릴산의 합성에 관한 것이다. Mo-V-W-O(WVM), Mo-V-O/Mo-W-O(VM/WM), Mo-W-O/Mo-V-O(WM/VM) 그리고 Mo-V-O와 Mo-W-O의 기계적 혼합물 촉매(M-VM+WM)를 제조하여 BET, XRD, SEM, EPMA로 특성분석을 실시하였고 이들 촉매의 활성을 고정층 연속반응기에서 조사하였다. WVM 촉매의 경우 VM 촉매에 첨가된 소량의 텅스텐은 비표면적과 아크릴산의 선택도를 증가시켰으나 과량의 텅스텐은 아크로레인의 반응속도와 선택도를 감소시켰다. 담체로 사용한 WM 위에 VM이 존재하는 VM/WM 촉매의 활성과 선택도가 VM을 담체로 사용한 WM/VM 촉매보다 우수한 것으로 나타났고 WM과 VM의 기계적 혼합물 촉매는 상간협동 현상이 관찰되어 WM이나 VM 촉매보다 높은 수율을 나타내었다.

• 공업화학
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• 제5권2호
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• pp.295-304
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• 1994

담지촉매인 $Mo-V-O/SnO_2$(VM/Sn)와 $SnO_2/Mo-V-O$(Sn/VM) 촉매를 제조하여 XRD, BET, SEM, $NH_3$, TPD 등으로 특성분석을 실시하였다. 고정층 연속 반응기에서 아크롤레인의 산화반응을 수행한 결과 이들 촉매의 아크롤레인 전화율과 아크릴산 수율이 Mo-V-O 자체보다 높았다. 이와 같은 상승효과의 원인을 TPD, TPR, TPO 등의 방법으로 고찰한 결과 Mo-V-O와 $SnO_2$의 접촉면에서 Mo-V-O가 $SnO_2$ 상으로 전자를 전달하고 $SnO_2$는 spill-over oxygen을 Mo-V-O 상으로 전달함으로써 반응에 의하여 부분환원된 Mo-V-O의 재산화를 촉진시키는 상간협동 현상이 존재하기 때문으로 판단되었다.

• 공업화학
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• 제23권3호
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• pp.348-351
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• 2012

본 연구에서는 NO의 저온 SCR 반응에서 구리 첨가가 $Mn/CeO_2-ZrO_2$ 촉매의 활성에 미치는 영향을 알아보았다. 이를 위하여 $Mn/CeO_2-ZrO_2$ 촉매에 구리가 각각 5, 10, 15 wt% 첨가된 세가지 촉매의 활성을 조사하였다. 촉매의 특성은 BET, XRD, XPS, $H_2-TPR$을 통해 분석하였다. 구리가 첨가된 촉매의 질소산화물 저감 효율을 측정한 결과 Cu 농도가 증가할수록 활성이 증가하였으며 Cu 15 wt%가 담지하였을 경우 질소산화물 저감효율이 99%까지 도달하는 등 가장 높은 저감효율을 나타내었다. 이는 표면의 망간과 구리의 interaction에 의한 환원의 향상이 촉매 효율 증가의 원인으로 여겨진다.

• 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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• 제47권5호
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• pp.401-406
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• 2010

For the lower-temperature preparation of calcium monoaluminate(CA, C:CaO, A:$Al_2O_3$) clinker which is hard to synthesize purely within its melting point, an equimolar hydrate was obtained and then used as a starting raw material of clinker burning. The hydrate was prepared from a mixture of waste oyster shell and industrial aluminium hydroxide by heating to $1200^{\circ}C$, grinding and mixing with water. The hydrate was composed of amorphous aluminium hydroxide and $C_3AH_6$(H:$H_2O$) formed by resolution-precipitation mechanism of the system C-A-H. By heating the hydrate, nearly pure and porous calcium monoaluminate clinker was formed at $1400^{\circ}C$ which is fairly lower temperature than that of its melting point. The formation of calcium monoaluminate was performed mainly by the reaction between amorphous alumina and $C_{12}A_7$ caused by the decomposition of $C_3AH_6$. The immediate and earlier formation of $C_{12}A_7$ seemed to be accelerated by not only high surface area and instability of the thermally decomposed hydrate but also the catalytic effect of water decomposed from the hydrate. The final calcium monoaluminate clinker was very porous because of the influence of highly porous shape of the thermally decomposed hydrate.

• 한국재료학회지
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• 제30권5호
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• pp.267-271
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• 2020

Cerium oxide (ceria, CeO₂) is one of the most wide-spread oxide supporting materials for the precious metal nanoparticle class of heterogeneous catalysts. Because ceria can store and release oxygen ions, it is an essential catalytic component for various oxidation reactions such as CO oxidation (2CO + O₂ 2CO₂). Moreover, reduced ceria is known to be reactive for water activation, which is a critical step for activation of water-gas shift reaction (CO + H₂O → H₂ + CO₂). Here, we apply van der Waals-corrected density functional theory (DFT) calculations combined with U correction to study the mechanism of water chemisorption on CeO₂(111) surfaces. A stoichiometric CeO₂(111) and a defected CeO₂(111) surface showed different water adsorption chemistry, suggesting that defected CeO₂ surfaces with oxygen vacancies are responsible for water binding and activation. An appropriate level of water-ceria chemisorption energy is deduced by vdW-corrected non-local correlation coupled with the optB86b exchange functional, whereas the conventional PBE functional describes weaker water-ceria interactions, which are insufficient to stabilize (chemisorb) water on the ceria surfaces.

• 한국물환경학회지
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• 제34권6호
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• pp.621-631
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• 2018

In this study, catalyst was made through incipient wetness method using palladium (Pd) as noble metal, indium (In) as secondary metal, and montmorillonite (MK10) and Al pillared montmorillonite (Al-MK10) as supporters. The nitrate reduction rate of the catalysts was measured by batch experiments where H2 gas was used as reducing agent and formic acid as pH controller. Transmission electron microscopy (TEM) equipped with energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) were all used to determine the elemental distribution of Pd, In, Al, and Si on catalysts. It was observed that Al pillaring increased the Al/Si elemental composition ratio and point of zero charge of MK10, but decreased its BET specific surface area and pore volume. The nitrate reduction rate of Al-MK10 Pd/In was 2.0 ~ 2.5 times higher than that of MK10 Pd/In using artificial groundwater (GW) in ambient temperature and pressure. Nitrate reduction rates in GW were 1.2 ~ 1.7 times lower than those in distilled deionized water (DDW). Nitrate reduction rates in acidic conditions were higher than those in neutral condition in both GW and DDW. The amount of produced NH3-N over degraded NO3- at acid conditions was lower than that of neutral condition. Even though the leaching of Pd after reaction was measured in DDW it was not detected when both Al-MK10 Pd/In and MK10 Pd/In were used in GW. The modification of montmorillonite as a supporter significantly increased the reductive catalytic activities of nitrates. However, the ratio of producing ammonia by-products to degraded nitrates in ambient temperature and pressure was similar.

• 청정기술
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• 제24권3호
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• pp.198-205
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• 2018

본 연구는 $Co-CeO_2$ 촉매의 $N_2O$ 분해 반응에서 촉매의 제조 방법이 활성에 미치는 영향을 고찰하였다. $Co-CeO_2$ 촉매는 공침법(Co-precipitation)과 함침법(Incipient wetness impregnation)으로 제조하였다. 제조된 촉매의 성능을 평가하기 위하여 $N_2O$ 직접 촉매 분해(Direct catalytic $N_2O$ decomposition) 반응을 $250{\sim}375^{\circ}C$에서 실시하였다. 그 결과 공침법으로 제조된 촉매(CoCe-CP)는 $O_2$ 및/또는 $H_2O$의 존재 하에서도 $N_2O$ 분해 반응에서 향상된 성능을 보인 반면에 함침법으로 제조된 촉매(CoCe-IM)는 그렇지 못하였다. 이러한 촉매 활성의 차이를 조사하기 위하여 XRD, BET, TEM, $H_2-TPR$, $O_2-TPD$ 그리고 XPS와 같은 촉매 특성 분석들을 진행하였다. 촉매의 제조 방법에 따라서 입자의 크기 및 표면적이 변화하는 것을 확인하였고 합성 과정이 촉매의 물리적 특성에 영향을 미치는 것을 알 수 있었다. 공침법으로 제조된 촉매의 활성 증가는 $Co^{3+}{\rightarrow}Co^{2+}$의 향상된 환원 특성 및 산소 탈착 속도 향상에 기인한 것으로 여겨진다. 하지만, $N_2O$ 분해와 관련이 있는 촉매의 표면 전하 상태 및 결합에너지는 제조 방법에 따라서 변하지 않는 것을 확인하였다.

• 대한환경공학회지
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• 제22권4호
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• pp.609-617
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• 2000

본 연구에서는 소각로용 SCR(Selective Catalytic Reduction) 촉매개발의 일환으로, 소각로 배기가스 중에 다량 함유되어 있는 염화수소 (HCl) 기체가 촉매활성에 미치는 영향에 관하여 고찰하였다. 연구에 사용된 촉매는 상용 $V_2O_5-WO_3/TiO_2$ 촉매와 구리이온이 교환된 모더나이트형 제올라이트, CuHM 촉매로 실험은 수분의 유무에 따라 건조가스 조건과 습윤가스 조건으로 나누어 수행하였다. 건조가스 조건에서는 염화수소농도가 증가함에 따라 CuHM 촉매의 NO 제거활성이 가역적으로 증가하는 반면 $V_2O_5-WO_3/TiO_2$ 촉매는 비가역적으로 저하되는 상반되는 결과를 보였다. 그리고 수분이 포함된 습윤가스 조건에서는 CuHM와 $V_2O_5-WO_3/TiO_2$ 촉매 모두 비가역적으로 활성이 감소됨이 관찰되었으나, 상대적으로 CuHM이 보다 안정적인 활성을 나타내었다. 이러한 활성변화는 $NH_3$ TPD(Temperature Programmed Desorption) 탈착곡선의 증가, 감소로부터 HCl에 따른 일시적인 산량 증가 또는 영구적인 산점의 변화와 관계됨을 알 수 있었다. 그리고 BET 및 ICP 분석을 통하여 염화수소기체에 의한 촉매의 표면적과 $Cu^{{+}{+}}$ 및 $V_2O_5$ 함유량의 변화를 관찰하였다. 이상의 연구결과로부터 HCl과 같은 산가스를 함유하고 있는 배기가스 중의 질소산화물을 제거할 경우 CuHM 촉매에 대한 선택적 촉매 환원공정의 적용 가능성을 확인할 수 있었다.