본 연구에서는 공정 간소화, 균일한 나노 입자 형성, 백금 저감 및 활용도를 높이기 위하여 원자층 증착법 (Atomic Layer Deposition, ALD)을 통하여 양이온 교환막 연료전지용 촉매를 제조하고 증착 온도에 따른 백금 입자 형성 거동 을 확인하였다. 증착 온도는 250 °C, 300 °C, 350 °C로 조절하여 백금 촉매를 형성하였으며 각 각의 촉매의 증착 양 상을 확인하기 위하여 Thermogravimetric analysis, X-ray diffraction 및 Transmission electron microscopy를 도입하여 담지량, 백금 입자 분포, 크기 및 결정구조 등을 확인하였다. 합성된 백금 촉매를 연료전지에 적용하기 위해서 Cyclic Voltammetry 기법을 통해서 전기화학적 활성 표면적를 구하고, Membrane Electrode Assembly 셀을 제작하여 전지 특성을 확보하였다. 최종적으로, 백금 촉매 제조 시 ALD 증착 온도는 300 °C 이하에서 합성해야 됨을 밝혀냈으며, ALD으로 제작된 백금 촉매가 기존 습식 촉매보다 더 우수한 특성을 보임을 확인하였다. 해당 연구는 ALD을 통하여 다양한 접근법으로 촉매를 제조할 시, 기본적인 ALD 공정 정보 및 ALD 촉매 합성 방향성을 제공할 수 있다.
고온에서 진행되는 프로판 탈수소 반응에서 촉매의 불활성화의 주된 원인은 코크 침적, 소결현상이 있다. 이러한 불활성화를 줄이는 촉매를 연구하기 위해, 본 연구에서는 열적 안정성이 높은 MgAl2O4를 담체로 적용하여 프로판 탈수소 반응용 촉매로의 활용성을 확인하고자 하였다. Alcohthermal method로 MgAl2O4를 소성온도 800, 900, 1000℃로 달리하여 제조하였고, Pt와 Sn을 공동함침법으로 담지하여 Pt-Sn/MgAl2O4촉매를 제조하였다. 열적안정성의 확인을 위해 반응온도를 고온의 650, 600℃에서 진행하였다. 반응실험 결과 반응온도에 상관없이 담체의 소성온도가 800℃인 담체적용 촉매일 때 프로판 탈수소 반응 실험의 전환율과 수율이 담체소성온도가 900,1000℃인 담체적용 촉매보다 높은 것을 확인하였고, 반응온도가 고온인 650℃일 때는 Pt-Sn/θ-Al2O3보다도 더 높은 수율을 가지는 것을 볼 수 있었다. 특성분석으로는 TGA, BET, XRD, CO-화학흡착, SEM-EDS 분석을 실시하였다. MgAl2O4-800oC가 좋은 수율과 Pt분산도 및 적은 불활성화 정도의 관계를 서로 연관 지어 확인하였다.
To improve its textural properties as a support for platinum catalyst, carbon aerogel was chemically activated with KOH as a chemical agent. Carbon-supported platinum catalyst was subsequently prepared using the prepared carbon supports(carbon aerogel(CA), activated carbon aerogel(ACA), and commercial activated carbon(AC)) by an incipient wetness impregnation. The prepared carbon-supported platinum catalysts were applied to decalin dehydrogenation for hydrogen production. Both initial hydrogen evolution rate and total hydrogen evolution amount were increased in the order of Pt/CA < Pt/AC < Pt/ACA. This means that the chemical activation process served to improve the catalytic activity of carbon-supported platinum catalyst in this reaction. The high surface area and the well-developed mesoporous structure of activated carbon aerogel obtained from the activation process facilitated the high dispersion of platinum in the Pt/ACA catalyst. Therefore, it is concluded that the enhanced catalytic activity of Pt/ACA catalyst in decalin dehydrogenation was due to the high platinum surface area that originated from the high dispersion of platinum.
Electricity is generated by the combined reactions of hydrogen oxidation and oxygen reduction which occur on the Pt/C catalyst surface. There have been lots of researches to make high performance catalysts which can reduce Pt utilization. However, most of catalysts are synthesized by wet-processes and a significant amount of chemicals are emitted during Pt/C synthesis. In this study, Pt/C catalyst was produced by arc plasma deposition process in which Pt nano-particles are directly deposited on carbon black surfaces. During the process, islands of Pt nano-particles were produced and they were very fine and well-distributed on carbon black surface. Compared with a commercialized Pt/C catalyst (Johnson & Matthey), finer particle size, narrower size distribution, and uniform distribution of APD Pt/C resulted in higher electrochemical active surface area even at the less Pt content.
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.
The Pt-Ru/Carbon as an anode catalyst supported on the commercial activated carbon (AC) having high surface area and micropore was characterized for application of Direct Methanol Fuel Cell (DMFC). The Pt-Ru/AC anode catalyst used in this experiment showed the performance of 600 mA/cm2 current density at 0.3 V. The borohydride reduction process using NaBH4, denoted as a process A, showed much higher current and power densities than process B prepared by changing the reduction and washing process of process A. The particle sizes are strongly affected by the reduction process than the specific surface area of raw active carbon and the sizes are almost constant when the specific surface area of carbon are over than the 1200 m2/g. Smaller particle size of catalyst and more narrow intercrystalite distance increased the performance of DMFC.
Electrochemical promotion of the reaction rate was investigated for CO oxidation in a solid electrolyte catalytic reactor where a thin film of Pt was deposited on the yttria stabilized zirconia as an electrode as well as a catalyst. It was shown under open circuit condition that potential was a mixed potential of O2exchange reaction and electrochemical reaction induced by CO. The effect of electrochemical modification on the CO oxidation rate was studied at various overpotentials and PCOPO2.
TiO2- and SiO2-supported Co3O4, Pt and Co3O4-Pt catalysts have been studied for CO and C3H8 oxidations at temperatures less than 250℃ which is a lower limit of light-off temperatures to oxidize them during emission test cycles of gasoline-fueled automotives with TWCs (three-way catalytic converters) consisting mainly of Pt, Pd and Rh. All the catalysts after appropriate activation such as calcination at 350℃ and reduction at 400℃ exhibited significant dependence on both their preparation techniques and supports upon CO oxidation at chosen temperatures. A Pt/TiO2 catalyst prepared by using an ion-exchange method (IE) has much better activity for such CO oxidation because of smaller Pt nanoparticles, compared to a supported Pt obtained via an incipient wetness (IW). Supported Co3O4-only catalysts are very active for CO oxidation even at 100℃, but the use of TiO2 as a support and the IW technique give the best performances. These effects on supports and preparation methods were indicated for Co3O4-Pt catalysts. Based on activity profiles of CO oxidation at 100℃ over a physical mixture of supported Pt and Co3O4 after activation under different conditions, and typical light-off temperatures of CO and unburned hydrocarbons in common TWCs as tested for C3H8 oxidation at 250℃ with a Pt-exchanged SiO2 catalyst, this study may offer an useful approach to substitute Co3O4 for a part of platinum group metals, particularly Pt, thereby lowering the usage of the precious metals.