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

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Oxidation Characteristics of Low Concentration CO Gas by the Natural Manganese Dioxide(NMD) in a Fixed Bed (고정층 반응기에서 망간광석(NMD)을 이용한 저농도 일산화탄소 산화특성)

  • Lee, Young Soon;Park, Jong Soo;Oh, Kwang Joong
    • Clean Technology
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    • v.2 no.1
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    • pp.60-68
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    • 1996
  • The oxidation of carbon monoxide of low concentration on the natural manganese dioxide (NMD) has been investigated in a fixed bed reactor. The experimental variables were concentration of oxygen (500ppm~99.8%) and carbon monoxide (500ppm~10000ppm) and catalyst temperature ($50{\sim}750^{\circ}C$). The NMD(Natural Manganese Dioxide) has been characterized by temperature - program reduction(TPR) using 2.4% $CO/H_2$ as a reducing agent, thermogravimetric analysis (TGA), and reduction of NMD by 2.4% $CO/H_2$. It was found that the NMD catalyst activity on the unit area was greater than the $MnO_2$ catalyst for oxidation of CO at the same temperature. The thermal stability of oxidation activity was considered to be maintained when the NMD was heated to $750^{\circ}C$. The TGA, reduction by CO, and TPR of the NMD showed that the NMD had active lattice oxygen which was easily liberated on heating in the absence and low concentration of oxygen. The reaction order in CO is 0.701 between 500~3500ppm and almost zero between 3500~10000ppm of CO.

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Oxidative Dehydrogenation of n-Butenes over BiFe0.65MoP0.1 Oxide Catalysts Prepared with Various Synthesis Method (다양한 합성 방법으로 제조된 BiFe0.65MoP0.1 산화물 촉매 상에서 n-부텐의 산화탈수소화 반응)

  • Park, Jung-Hyun;Shin, Chae-Ho
    • Korean Chemical Engineering Research
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    • v.53 no.3
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    • pp.391-396
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    • 2015
  • To investigate the effect of the catalyst synthesis method on the oxidative dehydrogenation (ODH) of nbutenes, $BiFe_{0.65}MoP_{0.1}$ oxide catalysts were prepared with various synthesis methods such as co-precipitation, citric acid method, hydrothermal method, and surfactant templated method. The catalysts were characterized by X-ray Diffraction (XRD), $N_2$ sorption, and $NH_3/1$-butene-temperature programmed desorption ($NH_3/1$-butene-TPD) to correlate with catalytic activity in ODH reaction. Among the catalysts studied here, $BiFe_{0.65}MoP_{0.1}$ oxide catalyst prepared with co-precipitation method marked the highest activity showing 1-butene conversion, 79.5%, butadiene selectivity, 85.1% and yield, 67.7% after reaction for 14 h. From the result of $NH_3$-TPD, the catalytic activity is closely related to the acidity of the $BiFe_{0.65}MoP_{0.1}$-x oxide catalyst and acidity of the $BiFe_{0.65}MoP_{0.1}$ oxde catalyst prepared with co-precipitation method was higher than that of other catalysts. In addition, combined with the 1-butene TPD, the higher catalytic activity is closely related to the amount of weakly adsorbed intermediate (< $200^{\circ}C$) and the desorbing temperature of strongly adsorbed intermediates (> $200^{\circ}C$).

Surface Segregation of Hydroniums and Chlorides in a Thick Ice Film at Higher Temperatures

  • Lee, Du Hyeong;Bang, Jaehyeock;Kang, Heon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.263-263
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    • 2013
  • This work examines the dynamic properties of ice surfaces in vacuum for the temperature range of 140~180 K, which extends over the onset temperatures for ice sublimation and the phase transition from amorphous to crystallization ice. In particular, the study focuses on the transport processes of excess protons and chloride ions in ice and their segregative behavior to the ice surface. These phenomena were studied by conducting experiments with a relatively thick (~100 BL) ice film constructed with a bottom $H_2O$ layer and an upper $D_2O$ layer, with excess hydronium and chloride ions trapped at the $H_2O$/$D_2O$ interface as they were generated by the ionization of hydrogen chloride. The migration of protons, chloride ions, and water molecules to the ice film surface and their H/D exchange reactions were measured as a function of temperature using the methods of low energy sputtering (LES) and Cs+ reactive ion scattering (RIS). Temperature programmed desorption (TPD) experiments monitored the desorption of water and hydrogen chloride from the surface. Our observations indicated that both hydronium and chloride ions migrated from the interfacial layer to segregate to the surface at high temperature. Hydrogen chloride gas desorbs via recombination reaction of hydronium and chloride ions floating on the surface. Surface segregation of these species is driven by thermodynamic potential gradient present near the ice surface, whereas in the bulk, their transport is facilitated by thermal diffusion process. The finding suggests that chlorine activation reactions of hydrogen chloride for polar stratospheric ice particles occur at the surface of ice within a depth of at most a few molecular layers, rather than in the bulk phase.

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Oxidation Reaction of $C_3H_6$ on Zinc Oxide (산화아연에서의 $C_3H_6$의 산화반응)

  • Hak Ze Chon;Chong Soo Han
    • Journal of the Korean Chemical Society
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    • v.25 no.2
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    • pp.92-96
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    • 1981
  • The reactions of adsorbed oxygen species, $O_2^-$ and $O^-$, with propylene on ZnO were studied by EPR spectroscopy and temperature programmed desorption technique. Propylene interacts with adsorbed $O_2^-$ at $25^{\circ}C$ and the surface intermediate was decomposed to CO, $H_2$, $CO_2$ and $CH_4$ by raising the temperature above $200^{\circ}C$, while $O^-$ gave the products of complete oxidation, $CO_2$ and $H_2O$ above $300^{\circ}C$.

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Growth of ${\gamma}$-Al2O3 (111) on an ultra-thin interfacial Al2O3 layer/NiAl(110)

  • Lee, M.B.;Frederick, B.G;Richardson, N.V.
    • Journal of Korean Vacuum Science & Technology
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    • v.2 no.2
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    • pp.63-77
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    • 1998
  • The oxidation of NiAl(110) was investigated in the temperature regime between 300K and 1300 K using LEED (low energy electron diffraction), TPD (temperature programmed desorption) and HREELS (high resolution electron energy loss spectroscopy). The adsorption of N2O and O2 up to reconstructions. Stepwise annealing of the oxygen-saturated sample from 600 K to 1300K in UHV (ultra-high vacuum,) results in firstly the onset of randomly oriented then finally fairly well-ordered. 5 ${\AA}$ Al2O3 film with quasi-hexagonal periodicity. Ordered thicker oxide films of 18-30 ${\AA}$ seem to be grown on this interfacial oxide layer by direct oxidation of sample at elevated temperature between 1150 and 1300 K because of the LEED pattern consisting of new broad hexagonal spots and the previous 5 ${\AA}$ spots. Although the periodicity of surface oxygen arrays shows no significant change from an hexagonal close-packing, the O-O distance changes from ∼3.0 ${\AA}$ film to ∼2.9 ${\AA}$ for thicker oxides. with the appearance of Auger parameter, for the 5${\AA}$ film can be described better as an interfacial oxide layer. The observation of three symmetric phonon peaks can be also a supporting evidence for this phase assignment since thicker oxide films on the Same Ni2Al3(110) show somewhat different phonon structure much closer to that of the ${\gamma}$-Al2O3. The adsorption/desorption of methanol further proves the preparation of less-defective and/or oxygen-terminated Al2O3 films showing ordered phase transitions with the change of oxide thickness between 5 ${\AA}$ to 30 ${\AA}$.

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Hydrogen Absorption by Crystalline Semiconductors: Si(100), (110) and (111)

  • Jeong, Min-Bok;Jo, Sam-Geun
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.02a
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    • pp.383-383
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    • 2010
  • Gas-phase hydrogen atoms create a variety of chemical and physical phenomena on Si surfaces: adsorption, abstraction of pre-adsorbed H, Si etching, Si amorphization, and penetration into the bulk lattice. Thermal desorption/evolution analyses exhibited three distinct peaks, including one from the crystalline bulk. It was previously found that thermal-energy gaseous H(g) atoms penetrate into the Si(100) crystalline bulk within a narrow substrate temperature window(centered at ~460K) and remain trapped in the bulk lattice before evolving out at a temperature as high as ~900K. Developing and sustaining atomic-scale surface roughness, by H-induced silicon etching, is a prerequisite for H absorption and determines the $T_s$ windows. Issues on the H(g) absorption to be further clarified are: (1) the role of the detailed atomic surface structure, together with other experimental conditions, (2) the particular physical lattice sites occupied by, and (3) the chemical nature of, absorbed H(g) atoms. This work has investigated and compared the thermal H(g) atom absorptivity of Si(100), Si(111) and Si(110) samples in detail by using the temperature programmed desorption mass spectrometry (TPD-MS). Due to the differences in the atomic structures of, and in the facility of creating atom-scale etch pits on, Si(100), (100) and (110) surfaces, the H-absorption efficiency was found to be larger in the order of Si(100) > Si(111) > Si(110) with a relative ratio of 1 : 0.22 : 0.045. This intriguing result was interpreted in terms of the atomic-scale surface roughening and kinetic competition among H(g) adsorption, H(a)-by-H(g) abstraction, $SiH_3(a)$-by-H(g) etching, and H(g) penetraion into the crystalline silicon bulk.

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Selective Catalytic Oxidation of Ammonia over Noble Catalysts Supported on Acidic Fe-ZSM5 Supports (산성 Fe-ZSM5 담체에 담지된 귀금속 촉매를 활용한 암모니아의 선택적 산화반응)

  • Kim, Min-Sung;Lee, Dae-Won;Lee, Kwan-Young
    • Clean Technology
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    • v.18 no.1
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    • pp.89-94
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    • 2012
  • In this study, we investigated the activity of Pd and Pt supported on acidic Fe-ZSM5 supports for selective catalytic oxidation of ammonia ($NH_3$-SCO). Among the catalysts, Pt/Fe-ZSM5 catalyst exhibited superior $NH_3$-SCO activity to Pd/Fe-ZSM5 catalyst. We also tested Pt/Fe-ZSM5 catalysts with different Fe loading using ion-exchange method to prepare Fe-ZSM5 supports, which resulted in the increased catalytic performance with smaller Fe content: $NH_3$ was oxidized completely at low temperature ($250^{\circ}C$). The physicochemical properties of Fe-ZSM5 were investigated to figure out the relationship between the characteristics of the catalysts and the catalytic activity on $NH_3$-SCO by Inductively coupled plasma-atomic emissions spectrometer (ICP-AES), $N_2$ sorption, X-ray diffraction (XRD), temperature programmed desorption of $NH_3$ ($NH_3$-TPD) technique.

The Effect of Dealumination on the Structure and Acidity of SAPO-11 Molecular Sieve (탈알루미늄화가 SAPO-11 분자체의 구조 및 산성도에 미치는 영향)

  • Park, Jong Yul;Lee, Chi Hun;Kim, Soo Kyung
    • Journal of the Korean Chemical Society
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    • v.40 no.3
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    • pp.202-208
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    • 1996
  • SAPO-11 was synthesized hydrothermally and dealuminated with $H_4$EDTA. The framework structure of SAPO-11 was maintained safely by 24 hours' dealumination, but further dealumination for 48 hours caused SAPO-11 collapsed and to be changed to variscite($AIPO_4{\cdot}2H_2O$) and tridymite($SiO_2$). Dealuminated SAPO-11 showed two structural hydroxyl bands at 3607 $cm^{-1}$ and 3453 $cm^{-1}$ respectively. The intensities of these two bands increased according to the extent of dealumination, and disappeared by the adsorption of methylamine. Dealuminated SAPO-11 showed higher desorption temperatures and greater activation energies in desorption of water and methylamine compared to non-dealuminated SAPO-11. All the phenomena may be due to the stronger interactions of Bronsted acid sites of structural hydroxyl groups generated by dealumination with adsorbed water and methylamine molecules respectively.

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Effect of Reaction Conditions for n-Butane Dehydrogenation over Pt-Sn/θ-Al2O3 Catalyst (Pt-Sn/θ-Al2O3 촉매상에서 반응조건에 따른 n-부탄의 탈수소화 반응)

  • Cho, Kyung-Ho;Kang, Seong-Eun;Park, Jung-Hyun;Cho, Jun-Hee;Shin, Chae-Ho
    • Clean Technology
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    • v.18 no.2
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    • pp.162-169
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    • 2012
  • Pt-Sn/${\theta}-Al_2O_3$ catalyst for n-butane dehydrogenation reaction was prepared by incipient wetness method. To confirm the physicochemical properties of Pt-Sn/${\theta}-Al_2O_3$ catalyst, the characterization was performed using X-ray diffraction (XRD), $N_2$ sorption analysis, temperature programmed desorption of $NH_3$ ($NH_3$-TPD), temperature programmed reduction of $H_2$ ($H_2$-TPR) techniques. Also, the catalytic activities of Pt-Sn/${\theta}-Al_2O_3$ for n-butane dehydrogenation was tested as a function of pretreatment temperature, pretreatment time, reaction temperature, and the partial pressure of n-butane and hydrogen. The sum of selectivities to n-butenes consisting of 1-butene, cis-2-butene, and trans-2-butene was almost constant 95% in the range of conversion of n-butane 5-55%. The activation energy calculated from Arrhenius equation was $82.4kJ\;mol^{-1}$ and the reaction orders of n-butane and hydrogen from Power's law were 0.70 and -0.20, respectively.

An analysis on the impurities generated by discharge in AC plasma display panel (교류 플라즈마 표시기 방전 시 발생하는 불순물 종의 분석)

  • 김광남;김중균;양진호;황기웅;이석현
    • Journal of the Korean Vacuum Society
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    • v.8 no.4A
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    • pp.482-489
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    • 1999
  • AC PDP(P1asma Display Pane1)s use the mixture of inert gases to generate a discharge inside the display pixels. Impurities such as CO, $CO_2$ and OH inside discharge region may deteriorate the characteristics of PDP operation during long life time of PDP. Electro-negative gas such as CO can cause the sustain pulse amplitude to rise by attaching electrons which will play an important role in the earlier stage of the discharge. MgO film is used to protect the dielectric layer in AC PDP, and is in contact with the free space of display pixel where it is filled with the inert gas mixture. So, MgO film can be a main source of impurities. In this experiment, we observed the change of impurity generation of various MgO films which were deposited by different methods, by using QMS. (quadropole mass spectrometer) The main impurites were $H_2$, CO and $CO_2$. And with the comparison of the TPD (temperature programmed desorption) result, it can be understood that impurity gases are generated by sputtering of MgO surface not by outgassing. Deposition method had effects on the characteristics of the impurity generation. The MgO film manufactured by e-beam evaporation generated more amount of impurity gases than the MgO films manufactured by sputtering or ion-plating. And also heat treatment of MgO film after deposition decreased the magnitude of impurity gas generation.

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