• Title/Summary/Keyword: Temperature programmed desorption

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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
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.08a
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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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Thermal Decomposition of Octanethiolate Self-Assembled Monolayers on Cu(111) in UHV

  • Sung, Myung-M.;Yun, Won-J.;Lee, Sun-S.;Kim, Yun-Soo
    • Bulletin of the Korean Chemical Society
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    • v.24 no.5
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    • pp.610-612
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    • 2003
  • Octanethiol ($CH_3(CH_2)_7SH$) based self-assembled monolayer on Cu(111) in ultra-high vacuum has been examined using x-ray photoelectron spectroscopy (XPS), temperature programmed desorption (TPD), intergrated desorption mass spectrometry (IDMS), and contact angle analysis. The results show that the octanethiolate monolayers similar to those on gold are formed on Cu(111). The monolayers are stable up to temperatures of about 480 K. Above 495 K the monolayers decompose via the γ-hydrogen elimination mechanism to yield 1-octene in the gas phase. The thiolate head groups on the copper surface change to Cu₂S following the decomposition of hydrocarbon fragments in the monolayers at about 605 K.

Preparation of Honeycomb Carbon Dioxide Adsorbent Impregnated $K_2CO_3$ and Its Characterization ($K_2CO_3$를 담지시킨 고체 허니컴 이산화탄소 흡수제의 제조 및 이의 특성 평가)

  • Lee, Dong-Chul;Kim, Jin-Bae;You, Yoon-Jong
    • Applied Chemistry for Engineering
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    • v.23 no.6
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    • pp.624-629
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    • 2012
  • To capture and recover carbon dioxide ($CO_2$), we impregnated honeycomb made of ceramic paper with $K_2CO_3$ and its absorption characteristics of $CO_2$ were investigated. The absorption amount of $CO_2$ on the honeycomb absorbent impregnated with $K_2CO_3$ was 13.8 wt% at a constant temperature ($70^{\circ}C$) and relative humidity (66%) condition. Because the absorption amount of $CO_2$ achieved almost the same loading ratio of $K_2CO_3$ (17.6 wt%), the absorption reaction of $CO_2$ by $K_2CO_3$ on the honeycomb absorbent seems to be going smoothly. In addition, $CO_2$ absorption breakthrough characteristics of the honeycomb absorbent were analyzed at the temperature range of $50{\sim}80^{\circ}C$, and the water vapor was fed to an absorption column before the feeding of $CO_2$ or simultaneously with $CO_2$. As a result, the absorption capacity of $CO_2$ was more enhanced using the water vapor supplying before $CO_2$ than that of simultaneous supplying. It was confirmed by temperature programmed desorption analysis that the $KHCO_3$ produced by the absorption reaction of $K_2CO_3$ and $CO_2$ is regenerated by the desorption of $CO_2$ at a temperature of about $128^{\circ}C$.

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

  • Kim, Hanna;Shin, Chae-Ho
    • Korean Chemical Engineering Research
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    • v.59 no.2
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    • pp.281-295
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    • 2021
  • In this study, the direct amination of ethanol was performed over impregnated Ni on SiO2-Al2O3 mixed oxide catalysts prepared by varying Si/(Si + Al) molar ratio to 30 mol%. To characterize the physico-chemical properties of the catalysts used, X-ray diffraction (XRD), N2-physisorption, temperature-programmed desorption of iso-propyl alcohol (IPA-TPD), temperature-programmed desorption of ethanol (EtOH-TPD), temperature-programmed reduction with H2 (H2-TPR), H2-chemisorption and transmission electron microscopy (TEM) were used. The acidic property was continuously increased until Si/(Si + Al) = 30 mol% in SiO2-Al2O3 mixed oxides used. The dispersion of Ni metal and surface area, acid characteristics of the supported Ni catalyst have a complex effect on the catalytic reaction activity. The low reduction temperature of nickel oxide and acidic properties were beneficial to the formation of acetonitrile. In terms of conversion of ethanol, Ni/SiO2-Al2O3 catalyst with a molar ratio of 10 mol% Si/(Si+Al) showed the highest activity and a volcanic curve based on it. The tendency of results were consistent in the metal dispersion and catalytic activity.

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.

The Effect of K Promoter on Ni-Co (Bimetallic) Catalyst for Dry Methane Reforming

  • Dharmasaroja, Nichthima;Phongaksorn, Monrudee;Tungkamani, Sabaithip;Ratana, Tanakorn;Sornchammi, Thana
    • International Journal of Advanced Culture Technology
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    • v.3 no.2
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    • pp.110-117
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    • 2015
  • 10 wt% (Ni-Co) catalysts with different Ni and Co content : 10%Ni, 9%Ni1%Co, 7%Ni3%Co, 5%Ni5%Co, 3%Ni7%Co, and 10%Co; were prepared using sol-gel method followed by incipient wetness impregnation method. To investigate the catalytic activity including the stability, dry methane reforming were demonstrated over the pelletized catalysts at $620^{\circ}C$ under atmospheric pressure in a $CH_4:CO_2:N_2$ feedstock for 360 min. The results showed that bimetallic catalysts with the Co content equal to or greater than 3% were more stable than monometallic catalysts (10%Ni and 10%Co). The temperature programmed hydrogenation interpreted that the additional of Co into Ni catalyst improved the carbon resistance from methane cracking. Promoted this type of bimetallic catalyst using 1wt% K (trimetallic catalyst) prevented the carbon formation on the catalyst. The temperature programmed desorption of $CO_2$ indicated that this trimetallic catalyst has a greater number of strong basic sites. Moreover, the appearance of K lowered the number of weak basic sites and decreased the conversion of methane by 12 %.

$NO_x$ Chemistry Over Rutile $TiO_2$(110) Surfaces

  • Kim, Yu-Gwon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.02a
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    • pp.131-131
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    • 2012
  • We present our recent temperature-programmed desorption (TPD) study on catalytic reductions of $NO_x$ such as NO, $NO_2$, and $N_2O$ over rutile $TiO_2$(110) surfaces. Our results indicate that $NO_2$/NO readily reacts to give NO/$N_2O$ desorption at the substrate temperature as low as 100 K/70 K. Interestingly, $N_2O$, however, does not dissociate into $N_2$ and $O_{BBO}$ over the oxygen vacancy on the $TiO_2$(110) surface. Successive reduction of NO and $NO_2$ into $N_2O$ and NO, respectively, leaves oxygen atoms on the $TiO_2$(110) surface in a form of $O_{ad}$, which can induce additional reductive channels of NO and $NO_2$ at higher temperatures up to 400 K. During the repeated TPD cycles of $NO_x$, our x-ray photoelectron spectroscopy (XPS) analysis indicates that no N atom accumulates on the $TiO_2$ surface.

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