• Title/Summary/Keyword: Temperature programmed-desorption (TPD)

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CO Oxidation Over Manganese Oxide Catalysts: Effect of Calcination Temperature (망간 산화물 촉매상에서 일산화탄소의 산화반응 : 소성온도의 영향)

  • Park, Jung-Hyun;Kim, Yun-Jung;Cho, Kyung-Ho;Kim, Eui-Sik;Shin, Chae-Ho
    • Clean Technology
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    • v.17 no.1
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    • pp.41-47
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    • 2011
  • [ $MnO_2$ ]catalysts were prepared by precipitation method using potassium manganate and manganese acetate. The effect of calcination temperatures of $MnO_2$ catalysts for CO oxidation has been studied and their physicochemical properties were studied by X-ray diffraction (XRD), $N_2$ sorption, temperature programmed reduction of $H_2$ ($H_2-TPR$), and temperature programmed desorption of CO (CO-TPD) techniques. $MnO_2$ calcined at $300^{\circ}C$ catalyst has a large surface area $181m^2/g$ having a narrow pore size distribution at 9 nm. The results of XRD and $H_2-TPR$ showed that the catalysts calcined at different temperatures showed mixed oxidation states of Mn such as $Mn^{4+}$ and $Mn^{3+}$. CO-TPD showed that the quantity of $CO_2$ desorbed was decreased with increasing the calcination temperatures. The catalytic activity over the catalyst calcined at $300^{\circ}C$ exhibited the highest conversion reaching to 100% at $200^{\circ}C$. $H_2O$ vapor showed an inhibiting effect on the efficiency of the catalyst because of co-adsorption with CO on the active sites of manganese oxide catalysts and the initial catalytic activity of CO oxidation could be regenerated by removing $H_2O$ vapor in the reactants.

Electronic structure and catalytic reactivity of model oxide catalysts

  • Kim, Yu-Gwon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.02a
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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 $TiO_2$(110) surface as a model oxide catalyst has been studied to understand the reaction mechanism employing the temperature-programmed desorption (TPD) technique. The $TiO_2$(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 $Ti^{3+}$ defects near the surface region and are found to be closely related to the catalytic activity of the $TiO_2$(110) surface.

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The Effect of the Crystalline Phase of Zirconia for the Dehydration of Iso-propanol (이소프로판올의 탈수반응에서 지르코니아 촉매의 결정상에 따른 영향)

  • Sim, Hye-In;Park, Jung-Hyun;Cho, Jun Hee;Ahn, Ji-Hye;Choi, Min-Seok;Shin, Chae-Ho
    • Korean Chemical Engineering Research
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    • v.51 no.2
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    • pp.208-213
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    • 2013
  • Zirconium hydroxide was synthesized by varying the aging time of the zirconyl chloride octahydrate at $100^{\circ}C$ in aqueous solution and the resulting hydroxides were calcined at $700^{\circ}C$ for 6 h to obtain the crystalline $ZrO_2$. The materials used in this study were characterized by differential thermal analysis (DTA), X-ray diffraction (XRD), $N_2$-sorption, transmission electron microscopy (TEM), $NH_3$ temperature-programmed desorption ($NH_3$-TPD), $CO_2$-TPD and iso-propanol TPD analyses to correlate with catalytic activity for the dehydration of iso-propanol. The pure tetragonal $ZrO_2$ phase was obtained after 24 h aging of zirconium hydroxide and successive calcination at $700^{\circ}C$. The increase of aging time showed the production of smaller particle size $ZrO_2$ resulting that the higher specific surface area and total pore volume. $NH_3$-TPD results revealed that the relative acidity of the catalysts increased along with the increase of aging time. On the other hand, the results of $CO_2$-TPD showed the reverse trend of $NH_3$-TPD results. The best catalytic activity for the dehydration of iso-propanol to propylene was shown over $ZrO_2$ catalyst aged for 168 h which had the highest $S_{BET}$ ($178\;m^2\;g^{-1}$). The catalytic activity could be correlated with high surface area, relative acidity and easy desorption of iso-propanol.

Reaction of NO on Vanadium Oxide Surfaces: Observation of the NO Dimer Formation

  • Jeong, Hyun-Suck;Kim, Chang-Min
    • Bulletin of the Korean Chemical Society
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    • v.28 no.3
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    • pp.413-416
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    • 2007
  • The adsorption and surface reactions of NO on a VO/V(110) surface have been investigated using X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure, and temperature programmed desorption (TPD) technique. NO is molecularly adsorbed on VO/V(110) at 80 K. As the surface coverage of NO increases, the NO dimer is formed on the surface at 80 K. Both NO and (NO)2 are adsorbed on the surface with the N-O bond perpendicular to the surface. (NO)2 decomposes at ~100 K and the reaction product is desorbed as N2O. Decomposition of NO takes place when the surface temperature is higher than 273 K.

Gas-phase Dehydration of Glycerol over Supported Silicotungstic Acids Catalysts

  • Kim, Yong-Tae;Jung, Kwang-Deog;Park, Eun-Duck
    • Bulletin of the Korean Chemical Society
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    • v.31 no.11
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    • pp.3283-3290
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    • 2010
  • The gas-phase dehydration of glycerol to acrolein was carried out over 10 wt % HSiW catalysts supported on different supports, viz. $\gamma-Al_2O_3$, $SiO_2-Al_2O_3$, $TiO_2$, $ZrO_2$, $SiO_2$, AC, $CeO_2$ and MgO. The same reaction was also conducted over each support without HSiW for comparison. Several characterization techniques, $N_2$-physisorption, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), the temperature-programmed desorption of ammonia ($NH_3$-TPD), temperature-programmed oxidation (TPO) with mass spectroscopy and CHNS analysis were employed to characterize the catalysts. The glycerol conversion generally increased with increasing amount of acid sites. Ceria showed the highest 1-hydroxyacetone selectivity at $315^{\circ}C$ among the various metal oxides. The supported HSiW catalyst showed superior catalytic activity to that of the corresponding support. Among the supported HSiW catalysts, HSiW/$ZrO_2$ and HSiW/$SiO_2-Al_2O_3$ showed the highest acrolein selectivity. In the case of HSiW/$ZrO_2$, the initial catalytic activity was recovered after the removal of the accumulated carbon species at $550^{\circ}C$ in the presence of oxygen.

Dehydration of D-xylose over SAPO Catalysts Synthesized with Various Structure Directing Agents (다양한 구조 유도제로 합성된 SAPO촉매를 이용한 자일로오스의 탈수화반응)

  • Kim, Saet Byul;You, Su Jin;Kim, Yong Tae;Chae, Ho-Jeong;Jeong, Soon-Yong;Park, Eun Duck
    • Korean Chemical Engineering Research
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    • v.48 no.6
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    • pp.684-689
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    • 2010
  • We synthesized a variety of SAPO catalysts with various structure directing agents by the hydrothermal method and applied them to the D-xylose dehydration. Single or mixtures of organic amines, viz. tetraethylammonium hydroxide(TEAOH), dipropylamine(DPA), diethylamine(DEA), morpholine and diethanolamine(DEtA) were used as structure directing agents. The $N_2$-isotherm, $NH_3$-temperature programmed desorption(TPD) and temperature programmed oxidation(TPO) were conducted to characterize SAPO catalysts. Among tested SAPO catalysts, the SAPO-34 synthesized with morpholine showed the highest furfural yield. The external surface area as well as the surface concentration of acid sites appeared to affect the catalytic activity for the dehydration of xylose into furfural.

Effect of Ca Ion on the SCR Reaction over VOx/TiO2 (Ca 이온이 VOx/TiO2 SCR 반응에 미치는 영향 연구)

  • Kim, Geo Jong;Hong, Sung Chang
    • Applied Chemistry for Engineering
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    • v.27 no.2
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    • pp.165-170
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    • 2016
  • In this study, we investigated the cause of the decrease in activities of $VO_x/TiO_2$ SCR catalyst used for the burner reactor at a scale of $150000Nm^3/hr$ using X-ray diffraction (XRD), brunauer-emmett-teller (BET), atomic emission spectroscopy inductively coupled plasma (AES ICP), $H_2$ temperature programmed reduction ($H_2$-TPR), and $NH_3$ temperature programmed desorption ($NH_3$-TPD) analysis. Since the crystallization of the $VO_x$ and phase transition of $TiO_2$ did not occur, it was concluded that the catalyst was not deactivated by the thermal effect. In addition, from the elemental analysis showing that a large quantity of calcium was detected but not sulfur, the deactivation process of the $VO_x/TiO_2$ SCR catalyst was mainly caused by Ca but not by $SO_2$. The calcium was also found to decrease the catalytic activity by means of reducing $NH_3$ adsorption.

Surface Reactions of Atomic Hydrogen with Ge(100) in Comparison with Si(100)

  • Jo, Sam Keun
    • Applied Science and Convergence Technology
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    • v.26 no.6
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    • pp.174-178
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    • 2017
  • The reactions of thermal hydrogen atoms H(g) with the Ge(100) surface were examined with temperature-programmed desorption (TPD) mass spectrometry. Concomitant $H_2$ and $CH_4$ TPD spectra taken from the H(g)-irradiated Ge(100) surface were distinctly different for low and high H(g) doses/substrate temperatures. Reactions suggested by our data are: (1) adsorbed mono(${\beta}_1$)-/di-hydride(${\beta}_2$)-H(a) formation; (2) H(a)-by-H(g) abstraction; (3) $GeH_3$(a)-by-H(g) abstraction (Ge etching); and (4) hydrogenated amorphous germanium a-Ge:H formation. While all these reactions occur, albeit at higher temperatures, also on Si(100), H(g) absorption by Ge(100) was not detected. This is in contrast to Si(100) which absorbed H(g) readily once the surface roughened on the atomic scale. While this result is rather against expectation from its weaker and longer Ge-Ge bond as well as a larger lattice constant, we attribute the absence of direct H(g) absorption to insufficient atomic-scale surface roughening and to highly efficient subsurface hydrogenation at moderate (>300 K) and low (${\leq}300K$) temperatures, respectively.

Ammonia Adsorption Capacity and Breakthrough Curve of Zeolitic Materials Synthesized from Coal Fly Ash (석탄 비산재로부터 합성된 제올라이트의 암모니아의 흡착용량 및 파과특성)

  • Park, Jong-Won;Lee, Chang-Han
    • Journal of Environmental Science International
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    • v.31 no.10
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    • pp.833-844
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    • 2022
  • A zeolite material with a Si/Al molar ratio of 1.2 was synthesized by changing the NaOH/CFA ratio of coal fly ash (CFA) via a fusion/hydrothermal reaction in the HD thermal power plant. The change in the crystal structure of the zeolite was confirmed using XRD and SEM, and the ammonia adsorption capacities of the synthesized zeolitic materials and a commercial zeolite (Na-A zeolite) were analyzed via an ammonia temperature-programmed desorption (NH3-TPD) process. The SEM and XRD results revealed out the zeolitic materials from the coal fly ash maintained a hexagonal Linde-type crystal structure similar to that of Na-A zeolite, but the crystallinity of the synthesized zeolitic material was reduced due to impurities. The NH3 adsorption capacity, determined from the NH3-TPD analysis of was 1.122 mmol/g of the synthesized zeolitic material, which was lower than the NH3 adsorption capacity of the Na-A zeolite.

Reactions of n-Butane of Pd-Zeolite Y Catalyst (Pd-Zeolite Y 촉매에서의 n-Butane의 반응)

  • Chon Hakze;Oh Seung Mo
    • Journal of the Korean Chemical Society
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    • v.23 no.3
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    • pp.161-164
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    • 1979
  • The effect of acidity and the metal surface area of the Pd loaded zeolite catalysts; prepared from $Ca^{2+}-,\;La^{3+}-,\;NH_4^+-$exchanged Y and dealuminated HY was studied for the reaction of n-butane. The amount of strong acid site determined by the temperature programmed desorption of ammonia increased in the order NaY < CaY < LaY. Total amount of acid site decreased with increasing degree of dealumination, but the portion of strong acid site increased with increasing $SiO_2/Al_2O_3$ ratio. The effective metal surface area determined by the CO adsorption technique was large for those zeolite catalysts having strong acidity. It was found that conversion of n-butane was strongly dependent on the acidity and the effective metal surface area of the catalysts. The fact that the conversion of n-butane was proportional to the effective metal surface area suggests that the dehydrogenation by metallic component is the primary step in the reaction of n-butane.

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