친전자성 치환반응을 통하여 제조된 술폰화 단량체와 비(非)술폰화 단량체의 직접 중합법을 통하여 서로 다른 술폰화도를 나타내는 술폰화 폴리아릴에테르술폰 공중합체를 합성하고, 이들로부터 직접 메탄올 연료전지용 이중층(層) 고분자 전해질 막을 제조하였다. 우수한 이온 전도특성을 나타내는 술폰화도 50%의 공중합체를 사용하여 전해질 막의 모체(母體) 전도층을 제조하고, 이들의 한쪽 표면에 술폰화도 10%의 공중합체를 도포한 후 건조하여 낮은 메탄올 투과 특성의 코팅층을 형성시켰다. 도포되는 공중합체의 질량비를 5~20%로 조절함으로써 코팅 층 두께에 따른 전해질 막의 특성 변화를 고찰하였으며, 형성된 코팅 층을 막-전극 접합체의 음극 면에 접합시켜 운전 시 메탄올 연료와 직접 접촉하도록 하였다. 이중층 형성 공정을 통하여, 단일 전해질 막과 동등한 수준의 이온 전도 특성을 유지하면서도, 전해질 막을 통한 메탄올 투과 특성이 현저히 개선된 우수한 효율의 고분자 전해질 막 제조가 가능하였다. 작동 온도 60°C, 2 M의 메탄올 공급 환경에서 수행된 연료 전지 성능 평가 결과, 막-전극 접합체 출력 밀도는 5%의 질량비에서 최대 134.01 mW/cm2였으며, 이로부터 상용 나피온 115 대비 105.5%의 향상된 성능 효율을 확인할 수 있었다.

곰취(Ligularia fischeri)의 이용성을 높이데 필요한 기초자료를 확보하고자 메탄올을 용매로 하여 추출 온도 및 시간에 따른 생리활성 효과를 조사하였다. 곰취 메탄올추출물 1,000mg·L-1에 함유된 총 페놀함량, 총플라보노이드 함량은 각각 75.8-297.7mg·L-1 and 45.6-173.6mg·L-1이었다. 추출온도와 시간은 총 페놀함량, 총 플라보노이드 함량, 전자공여 능 의 경우 95℃에서 6시간 동안 추출했을 때 가장 좋았다. 그러나 아질산염 소거능은 75℃에서 12시간 추출한 것에서 97.4%로 가장 높게 나타났다. 곰취 메탄을 추출물 200mg·L-1 및 400mg·L-1 농도는 각각 폐암과 위암세포 증식을 90% 이상 억제시켰다. 따라서 곰취는 높은 생리활성 기능을 나타내는 채소로 나타났으며, 곰취를 가공품으로 이용하기 위해 메탄올로 추출할 때는 95℃에서 6시간 정도 하는 것이 좋을 것으로 생각되었다.

The phytochemicals of many plants suggest their potential use as dietary supplements in cancer chemoprevention and chemotherapy. In the present study, antitumor activity of Cudrania tricuspidata, a plant native to East Asia, was investigated. Cell growth inhibition of the extract on HT-29 colorectal adenocarcinoma using MTT colorimetric assay was determined. Apoptosis on HT-29 cells was performed by DNA fragmentation analysis. PGE2 release was measured by enzyme immunoassay, because PGE2 is a key protumorigenic prostanoid in many human cancers. For the ROS scavenging activity, ROS level was detected by laser scanning confocal microscope. It was found that methanol extract of leaves inhibits cell viability by inducing apoptosis as evidenced by DNA fragmentation. Stem bark decreases synthesis of PGE2, inflammatory mediator. Fruits exhibited pronounced ROS scavenging activity. Taken together, these results suggest that Cudrania tricuspidata exerts growth inhibition and anti-oxidation on HT-29 cells through apoptosis, ROS scavenging respectively that it may have anti-cancer properties.

The studies on integrated operation of fuel cell with fuel processor are very essential prior to its commercialization. In this study, Polymer Electrolyte Membrane Fuel Cell (PEMFC) was operated with a fuel processor, which is mainly composed of two parts, methanol steam reforming reaction and preferential oxidation (PROX). In fuel processor, ICI 33-5 (CuO 50%, ZnO 33%, Al2O3 8%, BET surface area: 66 m2g-1) catalyst and CuO-CeO2 catalyst were used for methanol steam reforming, preferential oxidation (PROX) respectively. PEMFC was operated by hydrogen fuel generated from fuel processor. The resulting gas from PROX reactor is used to operate PEMFC equipped with our prepared anode and cathode catalyst. PtRu/C catalyst gives more tolerance to CO.

Carbon nanofiber (CNF) grown catalytically was chemically activated with KOH to attain structural change of CNF. The structural changes of CNF through KOH activation were investigated by using BET and SEM. From the results of BET, it was found that KOH activation was effective to develop particular sizes of pores on the CNF surface, increasing the surface area of CNF. Activated CNF was applied as an anode catalyst support of fuel cell. The effects of different activation conditions including the activation temperature and the activation time on the specific surface area of the CNF activated with KOH were investigated to obtain appropriate structure as a catalyst support. The 60 wt% Pt-Ru catalyst prepared was observed by using TEM and XRD.

Methanol and formaldehyde were produced directly by the partial oxidation of methane over mixed oxide catalysts. The catalysts were composed of Mo and Bi with late-transition metals, such as Mn, Fe, and Co. The reaction was carried out at 450℃, 50 bar in a fixed-bed differential reactor. The prepared catalysts were characterized by O2-TPD and BET apparatus. Among the catalysts used, the catalyst composed of 1:1:2.5 molar ratio of Mo:Bi:Mn showed the best methane conversion and methanol selectivity. The change in ratio of methane to oxygen affected at the conversion and selectivity, and the most proper ratio was 10:1.5. Methane conversion, methanol and formaldehyde selectivities increased with the surface areas of the catalysts. From the O2-TPD result, it was found that the oxygen species responsible for this reaction might be the lattice oxygen species desorbed at high temperature around 800℃.

Methanol and formaldehyde were produced directly by the partial oxidation of methane. The catalysts used were mixed oxides of late-transition metals, such as Mn, Fe, Co, Ni and Cu. The reaction was carried out at 450℃, 50 bar in a fixed-bed differential reactor. The prepared catalysts were characterized by XRD, TPD and BET apparatus. Of the catalysts, A-Mn0.2-6, which contains 0.2 mole of Mn and calcined at 600℃, showed the best catalytic activity: 3.7% methane conversion, and 30 and 28% methanol and formaldehyde selectivities, respectively. The catalytic activity was changed with the content of Mn and the calcination temperature. Catalytic activity increased with the specific surface areas of the catalysts. With XRD, it was found that the structure of the catalysts are changed with calcination temperature. Through O2-TPD experiment, it was found that the catalysts showing good catalytic activity showed O2 desorption peak around 800℃.

In the June, 1991, there was the explosion in which methanol rectified column as a part of the new surface active agent's manufacturing processes. The type of explosion was estimated as the 'detonation'. The methanol rectified column was ruined, and broken pieces of the column were scattered within 900m. Also, there were victims such as the two deads and thirteen wounded persons. The cause of the explosion was heat explosion by being concentrated locally from 0.1% to several tens% of supply fluid at Metal Hydroperoxide, which was produced by methanol and hydrogen peroxide used as the bleach of surface active agent, during the operation stoppage process of methanol rectified column.

본 연구에서는 SEBS와 여러 가지의 유기화물로 처리된 MMT type의 clay를 이용하여 SSEBS-clay 하이브리드 막을 용액법으로 제조하였다. clay의 함량은 5 phr로 고정하였다. 용액법을 사용하여 clay를 SEBS에 분산시켰으며, 제조된 SSEBS-clay 하이브리드에서 clay의 특성피크가 완전히 박리되거나 이동하는 XRD 결과로부터 고분자의 clay 층간삽입을 확인하였다. Clay의 종류에 따라서 제조된 SSEBS-clay 하이브리드 막의 가스투과도, 기계적 물성 및 열적 성질을 측정하였다. SSEBS-clay 하이브리드 막은 clay 자체의 도입과 층간거리의 확대로 기체분자의 tortuosity를 증가시켜서 가스투과도를 저하시키는 것을 확인하였다.

1991년 6월 신규 계면활성제 [a-SF]의 제조 공정의 하나인 메탄올 정류탑에 있어서 폭발사고가 발생했다. 폭발 형태는『폭굉』 이였다 라고 판단되어지고 정류탑은 대파되었으며 탑벽 파편은 대강 900m 범위로 비산되었고 사망자 2명, 부상자 13명의 피해를 입었다. 원인물질은 계면활성제의 표백으로 사용하는 메탄올과 과산화수소에 의해 미량 생성한 유기과산화물(Metal Hydroperoxide)에서 정류탑의 운전정지과정 중에 공급액의 부터 수십까지 국부적으로 농축되어져 열 폭발을 일으킨 것으로 추정 되어진다.

Platinum catalysts for the DMFC (Direct Methanol Fuel Cell) were impregnated on several carbon supports and their catalytic activities were evaluated with cyclic voltammograms of methanol electro-oxidation. To increase the activities of the Pt/C catalyst, carbon supports with high electric conductivity such as mesoporous carbon, carbon nanofiber, and carbon nanotube were employed. The Pt/e-CNF (etched carbon nanofiber) catalyst showed higher maximum current density of and lower on-set voltage of 0.54 V vs. NHE than the Pt/Vulcan XC-72 in methanol oxidation. Although the carbon named by CNT (carbon nanotube) series turned out to have larger BET surface area than the carbon named by CNF (carbon nanofiber) series, the Pt catalysts supported on the CNT series were less active than those on the CNF series due to their lower electric conductivity and lower availability of pores for Pt loading. Considering that the BET surface area and electric conductivity of the e-CNF were similar to those of the Vulcan XC-72, smaller Pt particle size of the Pt/e-CNF catalyst and stronger metal-support interaction were believed to be the main reason for its higher catalytic activity.

Methanol was synthesized by homogeneous and catalytic reactions of partial oxidation of methane. The effect of pressure, temperature and oxygen concentration on methanol synthesis was investigated. The catalyst used was Bi-Cs-Mg-Cu-Mo mixed oxide. The partial oxidation reaction was carried out in a fixed bed reactor at 20~46 bar and 450~480℃ and oxygen concentration of 5.3~7.7mol%. The results were compared with results of homogeneous reaction performed at the same conditions. Methane conversions of the homogeneous and catalytic reactions increased with temperature. Methanol selectivity of the homogeneous reaction decreased with increasing temperature. However, the methanol selectivity of catalytic reaction increased with temperature. For both homogeneous and catalytic reactions, the methane conversions were around 5%. This may be due to the low oxygen concentration. Methanol selectivity of the catalytic reaction was higher than that of homogeneous one.

본 연구에서는 polyvinylalcohol(PVA)의 hydroxyl 작용기와 sulfosuccinic acid (SSA)의 carboxylic acid 작용기의 반응을 통하여 열가교된 PVA막을 제조하였다. 설폰산기를 함유한 SSA는 PVA 매트릭스에 대한 가교제의 역할뿐만 아니라 수소이온의 전도도를 높이는 역할 모두를 수행하였다. PVA의 가교도(degree of crosslinking)는 SSA의 함량으로 조절하였고 가교밀도(crosslinking density)는 극성 및 비극성 용매를 이용하여 계산하였다. Xylene 및 benzene과 같은 비극성 용매를 사용한 경우 가교밀도는 SSA함량에 따라 증가하였다. 그러나, 물과 methanol과 같은 극성 용매를 사용한 경우 가교밀도는 SSA함량 20%까지 증가하다가 그 이상의 함량에서는 설폰산기의 영향으로 감소하였다. 가교도와 확산계수, 기계적 물성 및 전도도, 메탄올 투과도 등에 대한 PVA막의 특성을 평가하였고 이들 특성은 SSA함량에 의존하였다.

술폰화 폴리스티렌/테플론(Polystyrene/Teflon, 이하 'PS/PTFE'로 칭함) 복합막을 제조하여 직접 메탄을 연료전지용 막에 관한 특성을 조사하였다. 복합막은 다음과 같이 제조되었다. 먼저 다공성 테플론 필름에 styrene 단량체와 가교제인 diviny benzene (이하 'DVB'로 칭함)의 비율을 달리하면서, 개시제 2,2'-azobis(isobutylonitlie) (AIBN)와 함께 함침시킨 후 열을 가해 폴리스티렌/테플론 복합막을 제조하였다. 그 후 술폰화제인 chlorosulfonic acid와 1,2-dichloroethane혼합용액을 사용하여 술폰화된 복합막을 제조하였다. 제조된 복합막의 술폰화 전과 후의 물리화학적 구조는 ATR-FTIR, SEM, THF 및 물에 대한 함유율, 이들의 이온교환량을 통하여 확인하였다. 이러한 결과로부터 스티렌/디비닐벤젠의 비율에 따라 복합막이 성공적으로 제조되었음을 확인하였다. 또한 가교제인 디비닐벤젠의 함량이 높을수록, 가교도가 증가하여 물 및 THF에 대한 함유율이 감소하였다. 이온전도도, 메탄올투과도를 조사한 결과, 디비닐벤젠의 함량 증가와 함께 이온전도도는 감소하였으며, 메탄올 투과도가 감소하였다. 제조된 술폰화된 폴리스티렌/테플론 복합막은 Nafion(R) 과 비교할 만한 높은 이온 전도도(0.11∼0.08 S/cm, 25℃)를 보이면서 훨씬 낮은 메탄올 투과도(6.6×10-7∼1.3×10-7 cm2/s)를 나타내었다. 이러한 결과들은 본 연구에서 개발된 복합막이 직접 메탄올 연료전지에 적용될 가능성이 높다는 것을 보여준다.

Direct Methanol Fuel Cell (DMFC) is considered as a candidate technology for applications in stationary, transportation as well as electronic power generation purposes. To develop a high performance direct methanol fuel cell(DMFC), a competent electrolyte membrane is needed. The electrolyte membrane should be durable and methanol crossover must be low. One of the approaches to increase the stability of generally used polymer electrolyte membranes such as Nafion against swelling or thermal degradation is to bond it with an inorganic material physically or chemically. In Noritake Company, we have developed a novel method of reinforcing the polymer electrolyte matrix with inorganic fibers. Methanol crossover values measured were significantly lower than the original polymer electrolyte membranes. These fiber reinforced electrolyte membranes (FREM) were used for DMFC study and stable power output values as high 160 mW/cm2 were measured. The details of the characteristics of the membranes as well as I-V data of fuel cell stacks are detailed in the paper.