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  • 제목/요약/키워드: temperature programmed reaction

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Catalytic Reactions of Ethanol and Acetaldehyde Over TiO2-supported Gold Catalysts

  • 김정진;김유권
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2012년도 제42회 동계 정기 학술대회 초록집
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    • pp.264-264
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    • 2012
  • As an environment-friendly alternative energy resource, ethanol may be used to obtain hydrogen, a clean energy source. Thus, studies on catalytic reactions involving ethanol have been studied to understand the underlying principles in the reaction mechanism using various oxide-supported catalysts. Among them, Au-based catalysts have shown a superior activity in producing hydrogen gas. In the present study, Au/TiO2 catalysts were prepared by deposition-precipitation method to understand their catalytic activities toward ethanol and acetaldehyde with increasing gold loading, especially at the very low Au loading regime. A commercially available TiO2 (Degussa P-25) was employed and the Au loading was varied to 0, 0.1, 0.5, and 1.0 wt% respectively. The catalysts showed characteristic x-ray diffraction (XRD) features at 2θ=78.5 that could be assigned to the presence of gold nanoparticles. Its reactivity measurements were performed under a constant flow of ethanol and acetaldehyde at a flow rate of 0.6μmol/sec and the substrate temperature was slowly raised at a rate of 0.2 K/sec. We observed that the overall reactivity of the catalysts increased with increasing Au loading along with selectivity favoring dehydrogenation to product hydrogen gas. In addition, we disclosed various reaction channels involving competitive reaction paths such as dehydrogenation, dehydration, and condensation. In addition, subsequent reactions of acetaldehyde obtained from dehydrogenation of ethanol, were found to occur and produce butene, crotonaldehyde, furan, and benzene. Based on the results, we proposed overall reaction pathways of such reaction channels.

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Reaction of Methanol and Methyl Iodide on ZnO(0001) and ZnO(11-20) Single Crystal Surfaces

  • Doh, Won-Hui;Roy, Probir Chandra;Kim, Chang-Min
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2011년도 제41회 하계 정기 학술대회 초록집
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    • pp.214-214
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    • 2011
  • The adsorption and reactions of methanol and methyl iodide on ZnO(0001) and ZnO(11-20) single crystal surfaces have been investigated using the temperature programmed desorption (TPD) technique. The interaction of methanol and methyl iodide with ZnO is stronger on the polar ZnO(0001) surface than the non-polar ZnO(11-20) surface. On ZnO(0001), methanol is decomposed to produce formaldehyde and hydrogen. Two desorption features of formaldehyde and hydrogen are observed at around 500 and 580 K. The interaction of methanol and pre-adsorbed hydrogen has been also investigated. The reaction mechanism of methanol on ZnO will be proposed.

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Stoichiometry, Thermal Stability and Reducibility of Perovskite-Type Mixed Oxide LaBO3 (B = Fe, Co, Ni)

  • Park, Il-Hyun;Lee, Hyung-Pyo
    • Bulletin of the Korean Chemical Society
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    • 제9권5호
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    • pp.283-288
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    • 1988
  • The titled properties on reduction of the perovskite LaBO3 (B = Fe, Co, Ni) have been investigated by means of temperature-programmed reduction, isothermal reduction and X-ray diffraction methods. Nominal composition of LaFeO3.18,LaCoO3.00andLaNiO2.92 are determined. Reduction reaction of these mixed oxides differed according to B-site transition metal and thermal stability on reduction decreased as following order: LaFeO3.18 > LaCoO3.00 > LaNiO2.92. From the results of isothermal reaction, kinetics on reduction of the perovskite has been discussed in detail.

알칼리 금속 이온(Na, K)이 V/W/TiO2의 NH3-SCR 반응인자에 미치는 영향 (The Effect of Alkali Metal Ions (Na, K) on NH3-SCR Response of V/W/TiO2)

  • 여종현;홍성창
    • 공업화학
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    • 제31권5호
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    • pp.560-567
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    • 2020
  • 본 연구는 다양한 산업공정의 배가스 중 대표적인 활성저하 물질로 알려진 알칼리 금속[Na(Sodium)과 K(Potassium)]이 V/W/TiO2 촉매의 NH3-SCR 반응에 미치는 영향을 확인 하였다. 이에 따른 활성 저하 원인을 규명하고자 NO, NH3-TPD, DRIFT, H2-TPR 분석을 수행 하였다. 그 결과, 각 알칼리 금속은 촉매 피독으로 작용하여 NH3 흡착양이 저하되고, Na과 K은 촉매의 반응 활성에 기여하는 L산점과 B산점을 감소시켜 SCR 반응을 저하시킨다. H2-TPR 분석을 통하여 알칼리 금속은 V-O-V (bridge oxygen bond)와 V=O (terminal bond)의 환원 온도에 영향을 끼쳐, 환원 온도가 고온으로 올라가기 때문에 활성 저하 원인으로 판단된다.

Changes in the Surface Characteristics of Gas-atomized Pure Aluminum Powder during Vacuum Degassing

  • Yamasaki, Michiaki;Kawamura, Yoshihito
    • 한국분말야금학회:학술대회논문집
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    • 한국분말야금학회 2006년도 Extended Abstracts of 2006 POWDER METALLURGY World Congress Part2
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    • pp.1039-1040
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    • 2006
  • Vacuum degassing is essential in the preparation of RS P/M aluminum alloys to remove adsorbates and for the decomposition of hydrated-Al2O3 on the powder surface. Changes in the surface characteristics during vacuum degassing were investigated by X-ray photoelectron spectroscopy and temperature-programmed desorption measurement. Hydrated-Al2O3 decomposition to crystalline-Al2O3 and hydrogen desorption on the surface of argon gas-atomized aluminum powder occurred at 623 K and 725 K, respectively. This temperature difference suggests that the reaction converting hydrated-Al2O3 to crystalline-Al2O3 during vacuum degassing should be divided into the two reactions "2Al+Al2O33H2O2Al2O3+6Hsurf"and"6Hsurf3H2".

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A Study on the Sulfur-Resistant Catalysts for Water Gas Shift Reaction I. TPR Studies of Mo/γAl2O3 Catalysts

  • 박진남;김준희;이호인
    • Bulletin of the Korean Chemical Society
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    • 제19권12호
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    • pp.1363-1368
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    • 1998
  • Mo/γ-Al2O3 catalysts were prepared by impregnation method in various conditions to identify the states of surface Mo species. TPR (Temperature-Programmed Reduction) and Raman spectroscopy were applied to analyze the surface Mo species. TPR analysis revealed that MoO3 was reduced to Mo through MoO2, the intermediate state and the increase of Mo loading enhanced the reducibility of Mo oxide till the formation of monolayer coverage. High temperature calcination induced oxygen defects in MoO3 giving their unstable states for easier reduction. Raman spectroscopy analysis showed that the increase of Mo loading induced the polymeric Mo oxide.

K2CO3를 담지시킨 고체 허니컴 이산화탄소 흡수제의 제조 및 이의 특성 평가 (Preparation of Honeycomb Carbon Dioxide Adsorbent Impregnated K2CO3 and Its Characterization)

  • 이동철;김진배;유윤종
    • 공업화학
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    • 제23권6호
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    • pp.624-629
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    • 2012
  • 온실가스의 주요성분인 이산화탄소를 포집 및 회수하기 위해 세라믹 종이로 만든 허니컴에 K2CO3를 담지 시켜 이산화탄소 흡수특성을 알아보았다. 70C, 66% RH 항온항습 조건에서 K2CO3를 담지 시킨 허니컴 흡수제의 이산화탄소 흡수량은 13.8 wt%를 나타내었다. 이러한 결과는 K2CO3 담지율 17.6 wt%와 거의 동일한 수준으로서 허니컴 흡수제에 담지된 K2CO3의 흡수 반응이 원활하게 진행되었음을 확인할 수 있었다. 또한, 허니컴 흡수제를 충진한 반응기에 4.51% 이산화탄소와 수분 동시공급 또는 수분 선 공급 후 이산화탄소를 공급하여 5080C 범위에서 이산화탄소 흡수 후 파과특성을 분석하였다. 그 결과 수분을 먼저 공급한 후 건조된 이산화탄소를 공급했을 때 더욱 늦게 파괴되어 흡수 반응이 좋아짐을 알 수 있었다. 흡수제와 이산화탄소의 흡수 반응에서의 생성물인 KHCO3128C에서 이산화탄소를 탈착하여 재생된다는 것을 Temperature Programmed Desorption (TPD)분석 결과를 통해 확인할 수 있었다.

Ni/SiO2-Al2O3 복합 산화물 촉매 상에서 에탄올의 직접 아민화 반응에 의한 선택적 아세토니트릴 합성 (Selective Synthesis of Acetonitrile via Direct Amination of Ethanol Over Ni/SiO2-Al2O3 Mixed Oxide Catalysts)

  • 김한나;신채호
    • Korean Chemical Engineering Research
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    • 제59권2호
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    • pp.281-295
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    • 2021
  • Si/(Si + Al) 몰비를 30 몰%까지 변화시켜 제조한 SiO2-Al2O3 복합 산화물(SA) 상에 니켈을 함침법으로 제조한 촉매 상에서 에탄올의 아민화반응에 미치는 영향을 연구하였다. 제조된 촉매의 물리·화학적 특성을 알아보기 위하여 X-선 회절분석(XRD), N2 흡착분석, 이소프로판올 승온탈착(IPA-TPD), 에탄올 승온탈착(EtOH-TPD), 수소 승온환원(H2-TPR), H2 화학흡착, 투과전자현미경(TEM) 분석을 수행하였다. SA 복합 산화물 상에서 Si/(Si + Al) = 30 몰%가 될 때까지 지속적으로 산점이 증가하였다. 담지된 Ni 금속의 분산도, 비표면적 및 산 특성 등이 촉매 반응활성에 복합적으로 영향을 미쳤다. 산점 증가와 니켈 산화물의 낮은 환원 온도는 아세토니트릴 생성에 유리하게 작용하는 것으로 사료된다. 에탄올의 전환율 측면에서는 10 wt% Ni이 담지된 Si/(Si + Al) = 10 몰% 촉매가 가장 높은 전환율을 보였으며 이를 기준으로 화산형 형태를 나타냈고, Ni 금속 분산도와 경향이 일치했다.

Electronic structure and catalytic reactivity of model oxide catalysts

  • 김유권
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2009년도 제38회 동계학술대회 초록집
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    • pp.35-35
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    • 2010
  • Understanding the mechanistic details of heterogeneous catalytic reactions will provide a way to tune the selectivity between various competing reaction channels. In this regard, catalytic decomposition of alcohols over the rutile TiO2(110) surface as a model oxide catalyst has been studied to understand the reaction mechanism employing the temperature-programmed desorption (TPD) technique. The TiO2(110) model catalyst is found to be active toward alcohol dehydration. We find that the active sites are bridge-bonded oxygen vacancies where RO-H heterolytically dissociates and binds to the vacancy to produce alkoxy (RO-) and hydroxyl (HO-). Two protons adsorbed onto the bridge-bonded oxygen atoms (-OH) readily react with each other to form a water molecule at ~500 K and desorb from the surface. The alkoxy (RO-) undergoes decomposition at higher temperatures into the corresponding alkene. Here, the overall desorption kinetics is limited by a first-order decomposition of intermediate alkoxy (RO-) species bound to the vacancy. We show that detailed analysis on the yield and the desorption temperatures as a function of the alkyl substituents provides valuable insights into the reaction mechanism. After the catalytic role of the oxygen vacancies has been established, we employed x-ray photoelectron spectroscopy to further study the surface electronic structure related to the catalytically active defective sites. The defect-related state in valence band has been related to the chemically reduced Ti3+ defects near the surface region and are found to be closely related to the catalytic activity of the TiO2(110) surface.

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Thermal and Photochemistry of Methyl Iodide on Ice Film Grown on Cu(111)

  • Sohn, Young-Ku;White, John M.
    • Bulletin of the Korean Chemical Society
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    • 제30권7호
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    • pp.1470-1474
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    • 2009
  • Thermal and photochemistry of methyl iodide (CH3I)adsorbedonD2O ice film on Cu(111) at 100 K were studied using temperature-programmed desorption (TPD) time-of-flight mass spectrometry (TOF-MS), X-ray and ultraviolet photoelectron spectroscopies. On the basis of TPD, multilayer and monolayer CH3I molecules desorb from D2O ice layer at 120 and 130 K, respectively. Photo-irradiation at 100 K exhibits dramatic changes in the TPD and I 3d5/2XPSofCH3I on ice film, due to a dramatic dissociation of CH3I. The dissociation is likely activated by solvated electrons transferred from the metal substrate during photo-irradiation. No other photo-initiated reaction products were found within our instrumental detection limit. During photo-irradiation, the CH3I, CH3 and I could be trapped (or solvated) in ice film by rearrangement (and self-diffusion) of water molecules. A newly appeared parent molecular desorption peak at 145 K is attributed to trapped CH3I. In addition, the CH3 and I may diffuse through ice and chemisorb on Cu(111), indicated by TPD and I d5/2 XPS taken with photo-irradiation time, respectively. No molecular ejection was found during photo-irradiation at 100 K. The work functions for CH3I/Cu(111),D2O/Cu(111)andCH3I/D2O/Cu(111) were all measured to be about 3.9 eV, 1.0 eV downward shift from that of clean Cu(111).