This study analyzed the influence of ball size and process control agents on the refinement and dehydrogenation behavior of TiH2 powder. Powders milled using ZrO2 balls with diameters of 0.1 mm, 0.3 mm, and 0.3+0.5+1 mm exhibited a bimodal particle size distribution, of which the first mode had the smallest size of 0.23 μm for the 0.3 mm balls. Using ethanol and/or stearic acid as process control agents was effective in particle refinement. Thermogravimetric analysis showed that dehydrogenation of the milled powder started at a relatively low temperature compared to the raw powder, which is interpreted to have resulted from a decrease in particle size and an increase in defects. The dehydrogenation kinetics of the TiH2 powder were evaluated by the magnitude of peak shift with heating rates using thermogravimetric analysis. The activation energy of the dehydrogenation reaction, calculated from the slope of the Kissinger plot, was measured to be 228.6 kJ/mol for the raw powder and 194.5 kJ/mol for the milled powder. TEM analysis revealed that both the milled and dehydrogenated powders showed an angular shape with a size of about 200 nm.

This study investigated the effects of revolution speed and ball size in planetary milling on the microstructure and dehydrogenation behavior of TiH2 powder. The particle size analysis showed that the large particles present in the raw powder were effectively refined as the revolution speed increased, and when milled at 500 rpm, the median particle size was 1.47 μm. Milling with a mixture of balls of two or three sizes was more effective in refining the raw powder than milling with balls of a single size. A mixture of 3 mm and 5 mm diameter balls was the optimal condition for particle refinement, and the measured median particle size was 0.71 μm. The dependence of particle size on revolution speed and ball size was explained by changes in input energy and the number of contact points of the balls. In the milled powder, the endothermic peak measured using differential thermal analysis was observed at a relatively low temperature. This finding was interpreted as the activation of a dehydrogenation reaction, mainly due to the increase in the specific surface area and the concentration of lattice defects.

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.

금속 산화물과 혼합한 Pt-Sn/Al2O3 촉매의 프로판 탈수소 반응 성능의 향상 가능성에 대해 서 연구하였다. 금속 산화물로서 Cu-Mn/γ-Al2O3, Ni-Mn/γ-Al2O3, Cu/α-Al2O3를 제조하여 Pt-Sn/Al2O3 촉매와 혼합하고, 프로판 탈수소 반응 성능을 측정하였다. 이 결과들을 불활성 물질인 glass bead를 혼합한 Pt-Sn/Al2O3 촉매를 기준샘플로 삼아 비교하였다. 촉매와 금속산화물을 환원처리 하지 않고 반응 실험한 경우, 576.5℃에서 기준샘플의 전환율 8% 대비, Cu-Mn/γ-Al2O3를 혼합한 Pt-Sn/Al2O3 촉매가 14.9%의 높은 전환율과 96.8%의 선택도를 보였다. 촉매와 금속산화물을 환원 처 리하여 반응활성을 측정한 경우, Cu/α-Al2O3과 Pt-Sn/Al2O3의 혼합촉매가 기준샘플대비 초기에 높은 수율을 보였다. 그러나, 촉매를 환원 처리한 경우 전반적으로 전환율 상승이 크지 않았고, 이것으로 Cu-Mn/γ-Al2O3의 격자산소가 탈수소반응의 전환율 증가 영향을 주었음을 알 수 있었다.

Pt@Cu/C core-shell catalysts were successfully prepared by impregnation of a carbon support with copper precursor, followed by transmetallation between platinum and copper. The Pt@Cu/C core-shell catalysts retained a core of copper with a platinum surface. The prepared catalysts were used for hydrogen production through catalytic dehydrogenation of decalin for eventual application to an onboard hydrogen supply system. Pt@Cu/C core-shell catalysts were more efficient at producing hydrogen via decalin dehydrogenation than Pt/C catalysts containing the same amount of platinum. Supported coreshell catalysts utilized platinum highly efficiently, and accordingly, are lower-cost than existing platinum catalysts. The combination of impregnation and transmetallation is a promising approach for preparation of Pt@Cu/C core-shell catalysts.

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.