• Title/Summary/Keyword: catalytic acid - sites

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Thermal Stability of $MnOx-WO_3-TiO_2$ Catalysts Prepared by the Sol-gel Method for Low-temperature Selective Catalytic Reduction

  • Sin, Byeong-Gil;Lee, Hui-Su
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2011.10a
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    • pp.28.2-28.2
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    • 2011
  • The selective catalytic reduction (SCR) of NOx by $NH_3$ is well known as one of the most convenient, efficient, and economical method to prevent NOx emission in flue gas from stationary sources. The degradation of the reactivity is the obstacle for its real application, since high concentrations of sulfur dioxide and thermal factor would deactivate the catalyst. It is necessary to develop high stability of catalysts for low-temperature SCR. Among the transition metal oxides, $WO_3$ is known to exhibit high SCR activity and good thermal stability. The $MnOx-WO_3-TiO_2$ catalysts prepared by sol-gel method with various $WO_3$ contents were investigated for low-temperature SCR. These catalysts were observed in terms of micro-structure and spectroscopy analyses. The $WO_3$ catalyst as a promoter is used to enhance the thermal stability of catalyst since it increases the phase transition temperature of $TiO_2$ support. It was found that the addition of tungsten oxides not only maintained the temperature window of NO conversion but also increased the acid sites of catalyst.

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Improving Catalytic Efficiency and Changing Substrate Spectrum for Asymmetric Biocatalytic Reductive Amination

  • Jiang, Wei;Wang, Yali
    • Journal of Microbiology and Biotechnology
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    • v.30 no.1
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    • pp.146-154
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    • 2020
  • With the advantages of biocatalytic method, enzymes have been excavated for the synthesis of chiral amino acids by the reductive amination of ketones, offering a promising way of producing pharmaceutical intermediates. In this work, a robust phenylalanine dehydrogenase (PheDH) with wide substrate spectrum and high catalytic efficiency was constructed through rational design and active-site-targeted, site-specific mutagenesis by using the parent enzyme from Bacillus halodurans. Active sites with bonding substrate and amino acid residues surrounding the substrate binding pocket, 49L-50G-51G, 74M,77K, 122G-123T-124D-125M, 275N, 305L and 308V of the PheDH, were identified. Noticeably, the new mutant PheDH (E113D-N276L) showed approximately 6.06-fold increment of kcat/Km in the oxidative deamination and more than 1.58-fold in the reductive amination compared to that of the wide type. Meanwhile, the PheDHs exhibit high capacity of accepting benzylic and aliphatic ketone substrates. The broad specificity, high catalytic efficiency and selectivity, along with excellent thermal stability, render these broad-spectrum enzymes ideal targets for further development with potential diagnostic reagent and pharmaceutical compounds applications.

Catalytic Cracking of Triphenylmethane on Alumina Mixed with Mordenite Formed Secondary Pore (2차세공이 형성된 모더나이트와 알루미나를 혼합한 촉매상에서 Triphenylmethane의 분해반응)

  • Lee, Kyong-Hwan;Choi, Jun-Woo;Ha, Baik-Hyon
    • Applied Chemistry for Engineering
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    • v.8 no.6
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    • pp.1048-1053
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    • 1997
  • Modified mordenites by HF treatement, which have different $SiO_2/Al_2O_3$ ratio, and those mixed with $\gamma$-alumina are prepared and used for catalytic cracking of triphenylmethane(TPM) in micro-activity tester(MAT). Dealumination of mordenites decreased the acid content but developed secondary mesopores. The conversion and the selectivity of benzene over modified mordenites with the mesopores were increased. However, for the further dealuminated mordenites, they decreased due to the destruction of pore structure and low acid amount. Accordingly, the maximum cracking activity and the maximum selectivity of benzene were obtained about 17 $SiO_2/Al_2O_3$ ratio of modified mordenites. The modified mordenites mixed with alumina enhanced the cracking activity of TPM compared with the pure mordenites. It can be explained that TPM is cracked at active sites with in large pores of alumina firstly and further cracked into small molecules in zeolite pores as step mechanism of catalytic cracking.

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Preparation and Thermal Degradation Behavior of WO3-TiO2 Catalyst for Selective Catalytic Reduction of NOx (NOx 제거용 WO3-TiO2 계 SCR 촉매 제조 및 열적열화거동연구)

  • Shin, Byeongkil;Kim, Janghoon;Yoon, Sanghyeon;Lee, Heesoo;Shin, Dongwoo;Min, Whasik
    • Korean Journal of Metals and Materials
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    • v.49 no.8
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    • pp.596-600
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    • 2011
  • Thermal degradation behavior of a $WO_3-TiO_2$ monolithic catalyst was investigated in terms of structural, morphological, and physico-chemical analyses. The catalyst with 4 wt.% $WO_3$ contents were prepared by a wet-impregnation method, and a durability test of the catalysts were performed in a temperature range between $400^{\circ}C$ and $800^{\circ}C$ for 3 h. An increase of thermal stress decreased the specific surface area, which was caused by grain growth and agglomeration of the catalyst particles. The phase transition from anatase to rutile occurred at around $800^{\circ}C$ and a decrease in the Brønsted acid sites was confirmed by structural analysis and physico-chemical analysis. A change in Brønsted acidity can affect to the catalytic efficiency; therefore, the thermal degradation behavior of the $WO_3-TiO_2$ catalyst could be explained by the transition to a stable rutile phase of $TiO_2$ and the decrease of specific surface area in the SCR catalyst.

Reaction of 1-Butene on Cation-Exchanged Faujasite Type Zeolite Catalysts (양이온 교환된 Faujasite형 Zeolite 촉매에서의 1-Butene의 반응)

  • Hakze Chon;Yong-Ki Hong
    • Journal of the Korean Chemical Society
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    • v.21 no.2
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    • pp.89-93
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    • 1977
  • Faujasite type zeolite synthesized from kaolin minerals was cation-exchanged and the catalytic activities of $1-Butene{\rightarrow}2-butene$ took place readily even on zeolites having no strong acid sites. The order of activity for isobutene formation was La > H > Zn > Na-faujasite, La-faujasite showing much higher activity. The same trend was observed for propylene formation except that both La-and H-faujasite showed comparable activity. The results seem to indicate that the activities for 1-buten cracking and isomerization on zeolite are directly related to the strength and concentration of the acid sites on zeolites.

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Acid-Base Bifunctional Metal-Organic Frameworks: Green Synthesis and Application in One-Pot Glucose to 5-HMF Conversion

  • Zhang, Yunlei;Jin, Pei;Meng, Minjia;Gao, Lin;Liu, Meng;Yan, Yongsheng
    • Nano
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    • v.13 no.11
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    • pp.1850132.1-1850132.14
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    • 2018
  • The direct synthesis of metal-organic frameworks (MOFs) with acidic and basic active sites is challenging due to the introduction of functional groups by post-functionalization method often jeopardize the framework integrity. Herein, we report the direct synthesis of acid-base bifunctional MOFs with tuning acid-base strength. Employing modulated hydrothermal (MHT) approach, microporous MOFs named $UiO-66-NH_2$ was prepared. Through the ring-opening reaction of 1,3-propanesultone with amino group, $UiO-66-NH_2-SO_3H-type$ catalysts can be obtained. The synthesized catalysts were well characterized and their catalytic performances were evaluated in one-pot glucose to 5-HMF conversion. Results revealed the acid-base bi-functional catalyst possessed high activity and excellent stability. This work provides a general and economically viable approach for the large-scale synthesis of acid-base bi-functional MOFs for their potential use in catalysis field.

Effect of MCM-41 Preparation Methods on the Kinetics of Catalytic Pyrolysis of Linear Low Density Polyethylene (MCM-41 촉매 합성법이 선형 저밀도 폴리에틸렌의 촉매 열분해 동역학에 미치는 영향)

  • Park Young-Kwon;Kim Joo-Sik;Jeon Jong-Ki;Lim Jung Eun;Kim Ji Man;Yoo Kyung-Seun
    • Polymer(Korea)
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    • v.29 no.2
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    • pp.122-126
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    • 2005
  • The effect of Al-MCM-41 preparation methods on the catalytic degradation of linear low density polyethylene (LLDPE) was investigated. Al-MCM-41 catalysts were synthesized by direct method (Al-MCM-41-D) and post treatment method (Al-MCM-41-P) and their characteristics were elucidated by XRD, BET, $NH_3\;TPD,\;^{27}Al$ MAS NMR. TGA kinetic analysis showed that the catalytic activation energies of Al-MCM-41-D and Al-MCM-41-P were 191.54 and 114.26 kJ/mol, respectively. The higher catalytic activity of Al-MCM-41-P would be attributed to its smaller pore size as well as higher number of acid sites that are accessible.

Catalytic Upgrading of Bio-oil Produced from Japanese Larch over MCM-41 (MCM-41 촉매 상에서 일본 낙엽송으로부터 생성된 바이오 오일의 접촉 개질 반응)

  • Park, Hyun Ju;Jeon, Jong-Ki;Jung, Kyeong Youl;Ko, Young Soo;Sohn, Jung Min;Park, Young-Kwon
    • Korean Chemical Engineering Research
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    • v.45 no.4
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    • pp.340-344
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    • 2007
  • Catalytic upgrading of pyrolytic bio-oil produced from Japanes Larch was carried out over MCM-41 catalyst. Oil with enhanced stability was produced by the MCM-41 catalyst due to transform oxygen known as a main cause for the instability of bio-oil into $H_2O$, CO and $CO_2$. In addition, the MCM-41 catalyst produced the larger amount of phenolic compounds in the pyrolytic bio-oil product compared with that in the bio-oil produced without catalyst. Especially, the catalytic activity of Al-MCM-41 for the bio-oil upgrading was higher than that of Si-MCM-41 because Al-MCM-41 has the larger amount of acid sites. Also, the better reforming result was obtained when pyrolytic bio-oil vapor passed through catalytic layer rather than Japanese Larch was mixed with catalyst directly.

Comparative Modeling and Molecular Dynamics Simulation of Substrate Binding in Human Fatty Acid Synthase: Enoyl Reductase and β-Ketoacyl Reductase Catalytic Domains

  • John, Arun;Umashankar, Vetrivel;Krishnakumar, Subramanian;Deepa, Perinkulam Ravi
    • Genomics & Informatics
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    • v.13 no.1
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    • pp.15-24
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    • 2015
  • Fatty acid synthase (FASN, EC 2.3.1.85), is a multi-enzyme dimer complex that plays a critical role in lipogenesis. This lipogenic enzyme has gained importance beyond its physiological role due to its implications in several clinical conditions-cancers, obesity, and diabetes. This has made FASN an attractive pharmacological target. Here, we have attempted to predict the theoretical models for the human enoyl reductase (ER) and ${\beta}$-ketoacyl reductase (KR) domains based on the porcine FASN crystal structure, which was the structurally closest template available at the time of this study. Comparative modeling methods were used for studying the structure-function relationships. Different validation studies revealed the predicted structures to be highly plausible. The respective substrates of ER and KR domains-namely, trans-butenoyl and ${\beta}$-ketobutyryl-were computationally docked into active sites using Glide in order to understand the probable binding mode. The molecular dynamics simulations of the apo and holo states of ER and KR showed stable backbone root mean square deviation trajectories with minimal deviation. Ramachandran plot analysis showed 96.0% of residues in the most favorable region for ER and 90.3% for the KR domain, respectively. Thus, the predicted models yielded significant insights into the substrate binding modes of the ER and KR catalytic domains and will aid in identifying novel chemical inhibitors of human FASN that target these domains.

Interaction of ${\alpha}$-Ketoglutarate Dehydrogenase Complex with Allosteric Regulators Detected by a Fluorescence Probe, 1,1'-bi(4-aniline)naphthalene-5,5'-disulfonic acid, an Inhibitor of Catalytic Activity

  • Hong, Sung-Youl;Bak, Choong-Il;Ryu, Jae-Ha;Song, Byoung-J.;Huh, Jae-Wook
    • BMB Reports
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    • v.29 no.3
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    • pp.230-235
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    • 1996
  • The interaction of ${\alpha}-ketoglutarate$ dehydrogenase complex (${\alpha}-KGDC$) with a hydrophobic fluorescent probe [1,1'-bi(4-aniline)naphthalene-5,5'-disulfonic acid] (bis-ANS) was studied. The punfied ${\alpha}-KGDC$ was potently inhibited by bis-ANS with an apparent half maximal inhibitory concentration ($IC_{50}$) of 9.8 ${\mu}m$ at pH 8.0. The catalytic activities of both the E1o and E2o subunits were predominantly inhibited while that of the E3 component was hardly affected. The binding of bis-ANS to the enzyme caused a marked enhancement and blue shift from 523 nm to 482 nm in the fluorescence emission spectrum. The dissociation constant ($K_d$) and the number of binding sites (n) were calculated to be 0.87 mM and 158, respectively. Allosteric regulators such as purine nucleotides and divalent cations further increased the fluorescence intensity of the $bis-ANS-{\alpha}-KGDC$ binary complex. These data suggest that the binding of these allosteric regulators to ${\alpha}-KGDC$ may cause the conformational changes in the enzyme and that bis-ANS could be used as a valuable probe to study the interaction of the multi-enzyme complex and its allosteric regulators.

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