• 공업화학
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• 제8권4호
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• pp.582-588
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• 1997

고체산 촉매인 헤테로폴리산 촉매를 이용하여 대기오염 방지를 위한 옥탄가 향상제인 TAME, ETBE 및 MTBE 합성반응에 대한 실험을 고정층 상압유통식 반응장치에서 수행하였다. 일반적으로 TAME, ETBE 및 MTBE 합성반응에서 헤테로폴리산에 hetero원자와 poly원자를 치환시켜 비교한 결과, 배위된 poly원자가 W, hetero원자가 Si인 $H_4SiW_{12}O_{40}$ 촉매의 활성이 가장 우수하였고, 또한 치환된 금속에 따라 촉매의 활성이 달랐으며 이는 촉매의 산성질과 관련이 있음을 알 수 있었다. 헤테로폴리산 촉매를 이용한 합성반응에서 TAME 경우는 $FeHPW_{12}O_{40}$과 $K_3PM_{o12}O_{40}$이 비교적 활성이 좋았으나, ETBE나 MTBE 경우에 비해서는 다소 활성이 낮았다. 그리하여 본 연구에서는 활성이 좋은 헤테로폴리산 촉매들을 선정하여 각각에 대하여 1:1로 다음과 같이 혼합하여 $H_4SiW_{12}O_{40}$ : $Sr_2SiW_{12}O_{40}$, $H_4SiW_{12}O_{40}$ : $NaH_2PW_{12}O_{40}$, $Fe_{1.5}PW_{12}O_{40}$ : $Mg_2SiW_{12}O_{40}$ 및 $Mg_2SiW_{12}O_{40}$ : $Ba_2SiW_{12}O_{40}$ 실험한 결과, 혼합촉매들이 각각의 단일성분 촉매때보다 TBA의 전화율과 ETBE나 MTBE의 선택율이 더욱 향상되었음을 알 수 있었다.

• 멤브레인
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• 제19권2호
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• pp.96-103
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• 2009

본 연구에서는 poly(vinyl chloride) (PVC)가지형 공중합체 전해질과 헤테로폴리산(HPA)을 이용하여 유무기 합성 전해질막을 제조하였다. poly(vinyl chloride)-g-poly(styrene sulfonic acid) (PVC-g-PSSA)는 PVC의 이차 염소의 직접적인 개시를 이용한 atom transfer radical polymerization (ATRP)로 합성하였다. 이때, HPA 나노입자는 수소 결합을 통해 PVC-g-PSSA 가지형 공중합체와 결합하는 것을 FT-IR spectroscopy를 통하여 확인하였다. 전해질막의 수소이온 전도도는 HPA의 질량 분율이 0.3이 될 때까지 상온에서 0.049에서 0.068 S/cm로 증가하였다. 이것은 HPA 나노입자 고유의 전도도와 가지형 공중합체가 가지고 있는 술폰산의 강화된 산도 때문이라고 추정된다. 합습률은 HPA의 질량 분율이 0.45까지 증가할수록 130에서 84%로 감소하였다. 이것은 HPA나노입자와 고분자 메트릭스 사이의 수소 결합의 상호작용 때문에 물을 흡수하는 site의 수가 감소한 결과라고 볼 수 있다. 열중량 분석결과 HPA의 농도가 증가할수록 전해질막의 열적 안정성이 강화된다는 것을 알 수 있었다.

• 한국막학회:학술대회논문집
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• 한국막학회 2008년도 춘계 총회 및 학술발표회
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• pp.147-150
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• 2008

• 한국수소및신에너지학회논문집
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• 제16권1호
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• pp.40-48
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• 2005

Until recently, only perfluorinated ionomer membrane such as Nation and Aciflex practically could be successfully used in water splitting. However, these membrane are limited by high cost and loss of membrane performance such as proton conductivity at elevated temperature above 80$^{\circ}C$. The sulfonated aromatic polymers such as PEEK and PSf, polyimides, and polybenzimidazoles are expected to have lower production cost as well as satisfactory chemical and electrochemical properties. HPAs and sulfonated polymers could have a significant influence on water electrolysis performance at elevated temperatures above 80$^{\circ}C$, but these phenomena have received relatively little attention until now. Therefore, it would be desirable to investigate the interrelation between the HPA and sulfonated polymer, such as SPEEK. The SPEEK membrane were prepared by the sulfonation of PEEK, and HPA was blended with SPEEK to increase the mechanical strength and electrochemical characteristics. As a results, electrochemical characteristics such as proton conductivity and ion exchange capacity were improved with the addion of 0.5 g HPA. And the properties of polymer electrolyte, SPEEK/HPA were better than Nation membrane at elevated temperature above 80$^{\circ}C$.

• 한국수소및신에너지학회논문집
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• 제22권5호
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• pp.569-578
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• 2011

The $SiO_2$ membranes for polymer electrolyte membrane fuel cell (PEMFC) are preapared by electrospinning method. It leads to high porosity and surface area of membrane to accommodate the proton conducting materials. The composite membrane was prepared by impregnating of Nafion ionomer into the pores of electrospun $SiO_2$ membranes. The $SiO_2$:heteropolyacid (HPA) nano-particles as a inorganic proton conductor were prepared by microemulsion process and the particles are added to the Nafion ionomer. The characterization of the membranes was confirmed by field emission scanning electron microscope (FE-SEM), thermogravimetry analysis (TGA), and single cell performance test for PEMFC. The Nafion impregnated electrospun $SiO_2$ membrane showed good thermal stability, satisfactory mechanical properties and high proton conductivity. The addition of the $SiO_2$:HPA nano-particle improved proton conductivity of the composite membrane, which allow further extension for operation temperature in low humidity environments. The composite membrane exhibited a promising properties for the application in high temperature PEMFC.

• Journal of Photoscience
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• 제10권3호
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• pp.231-236
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• 2003

TiO$_2$ has been used as photocatalyst since two and half decades ago. The efficiency in its photocatalytic reactions has been improved by increasing the surface area of the photocatalyst by supporting fine TiO$_2$ particles on some porous materials. In this work, heteropolytungstic acid (HPA) - encapsulated into the titanium exchanged SBA-15 mesoporous materials (TiSBA-15) were prepared and characterized. Also their photocatalytic effects on decomposition of phenol were investigated and the photodecomposition rates of the phenol were observed to be increased by 2.5 8 fold, as compared to those observed in the presence of HPA-encapsulated SBA-15 or TiSBA-15 without HPA.

• 한국추진공학회:학술대회논문집
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• 한국추진공학회 2005년도 제25회 추계학술대회논문집
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• pp.229-232
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• 2005

인화점이 높은 합성 액체연료인 RJ-4의 제조공정 개선에 관한 연구를 수행하였다. 상용원료인 MCPD(Methylcyclopentadiene dimer)를 이용한 RJ-4 연료제조에서 헤테로폴리 텅스토인산 세슘염 촉매와 2단 열 조절반응기를 사용하여 1차, 2차 수소화 및 이성화반응이 1 단계 연속공정으로 가능함을 알 수 있었다. 또한 $AlCl_3$ 대신에 헤테로폴리산 세슘염을 이성화촉매로 사용시 exe-THDMCPD(Tetrahydrodimethylcyclopentadiene)을 얻는 속도가 더 빠르며, 생성물과의 분리가 용이하고, 폐산 발생이 없으므로 환경친화적인 공정임을 확인하였다.

• 한국수소및신에너지학회논문집
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• 제20권2호
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• pp.95-103
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• 2009

In order to improve the electrochemical, mechanical and electrocatalytic characteristics, engineering plastic of polyether ether ketone (PEEK) as polymer matrix was sulfonated (SPEEK) and the organic-inorganic blend composite membranes has been prepared by loading heteropoly acids (HPAs), including tungstophosphoric acid (TPA), molybdophosphoric acid (MoPA), and tungstosilicic acid (TSiA). And then these were covalently cross-linked (CL-SPEEK/HPA) as the electrolyte and MEA of polymer electrolyte membrane electrolysis (PEME). As a result, the optimum reaction conditions of CL-SPEEK/HPA was established and the electrochemical characteristics such as ion conductivity ($\sigma$) were in the order of magnitude: CL-SPEEK /TPA30 (${\sigma}=0.128\;S/cm^{-1}$) < /MoPA40 (${\sigma}=0.14\;S/cm^{-1})$ < /TSiA30 (${\sigma}=0.22\;S/cm^{-1}$) at $80^{\circ}C$, and mechanical characteristics such as tensile strength: CL-SPEEK /TSiA30 $\fallingdotseq$ /MoPA40 < /TPA30. Consequently, in regards of above characterisitics and oxidation durability, the CL-SPEEK/TPA30 exhibited a better performance in PEME than the others, but CL-SPEEK/MoPA40 showed the best electrocatalytic activity of cell voltage 1.71 V among the composite membranes. The dual effect of higher proton conductivity and electrocatalytic activity with the addition of HPAs, causes a synergy effect.

• 멤브레인
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• 제16권1호
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• pp.9-15
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• 2006

Polyvinylalcohol (PVA)을 전해질 막으로 이용하여 위하여 가교제로서 sulfosuccinic acid (SSA)와 무기물 첨가제로 phosphotungstic acid (PWA), silicotungstic acid (SiWA) 등의 HPA (heteropolyacid)를 사용하여 PVA/SSA/HPA 복합막을 제조하였다. PVA/SSA/HPA 복합막은 HPA의 농도가 증가함에 따라 함수율은 감소하였으나 IEC값은 증가하는 경향을 나타내었다. PVA/SSA/HPA 복합막의 XRD 분석 결과 HPA의 농도가 증가함에 따라 HPA가 복합막 속으로 잘 분산되는 것을 확인할 수 있었으며 HPA로서 PWA보다 SiWA의 분산성이 우수하였다. TGA 분석결과 PVA/SSA 복합막은 가교 결합으로 인하여 PVA 보다 열안정성이 우수하였으며 복합막의 HPA의 농도가 증가할수록 열안정성이 더욱 증대되는 것을 알 수 있었다. PVA/SSA/HPA 복합막의 메탄올 투과저항은 Nafion보다 현저히 우수하였으며 HPA의 농도가 증가할수록 메탄올의 투과도는 감소하였다.

• 한국수소및신에너지학회논문집
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• 제17권2호
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• pp.149-157
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• 2006

Hydrogen as new energy sources is highly efficient and have very low environmental emissions. The proton exchange membrane fuel cell (PEMFC) is an emerging technology that can meet these demands. Therefore, the preparation of stable polymeric membranes with good proton conductivity and durability are very important for hydrogen production via water electrolysis with PEM at medium temperature above $80^{\circ}C$. Currently Nafion of Dupont and Aciflex of Asahi, etc., solid polymer electrolytes of perfluorosulfonic acid membrane, are the best performing commercially available polymer electrolytes. However, these membrane have several flaws including its high cost, and its limited operational temperature above $80^{\circ}C$. Because of this, significant research efforts have been devoted to the development of newer and cheaper membranes. In order to make up for the weak points and to improve the mechanical characteristics with cross -linking, acid-base complexes were prepared by the combination PSf-co-PPSS-$NH_2$ with PEEK-$SO_3H$. The results showed that the proton conductivity decreased in 17.6% and 40% but tensile strength increased in 78% and 98%, about $20.65\;{\times}\;10^6N/m^2$, in comparison with SBPSf/HPA and SPEEK/HPA complex membrane.