• Advances in nano research
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• 제12권3호
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• pp.291-300
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• 2022

The behavior of hydrogen species on the surface of the catalyst during the Lewis acid transformation to form Brønsted acid sites over the spherical silica-supported WO_x catalyst was investigated. To understand the structure-activity relationship of Lewis acid transformation and hydrogen bonding interactions, we explore the potential of using the in situ diffuse reflection infrared Fourier transform spectroscopy (DRIFTS) with adsorbed ammonia and hydrogen exposure. From the results of in situ DRIFTS measurements, Lewis acid sites on surface catalysts were transformed into new Brønsted acid sites upon hydrogen exposure. The adsorbed NH₃ on Lewis acid sites migrated to Brønsted acid sites forming NH⁴⁺. The results show that the dissociated H atoms present on the catalyst surface formed new Si-OH hydroxyl species - the new Brønsted acid site. Besides, the isolated Si-O-W species is the key towards H-bond and Si-OH formation. Additionally, the H atoms adsorbed surrounding the Si-O-W species of mono-oxo O=WO₄ and di-oxo (O=)₂WO₂ species, where the Si-O-W species are the main species presented on the Inc-SSP catalysts than that of the IWI-SSP catalysts.

• Bulletin of the Korean Chemical Society
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• 제25권9호
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• pp.1355-1360
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• 2004

The oxidative decomposition of trichloroethylene (TCE) was investigated using palladium catalysts supported on pure and sulfated zirconia. The reactions were performed under dry and wet conditions in the temperature between 200 and $550^{\circ}C$ keeping GHSV of 14,000 $h^{-1}.$ The products such as $C_2Cl_4,\;C_2HCl_5,\;CO\;and\;CO_2$ were observed in the reaction. The addition of water in the feed affected the distribution of reaction product with dramatically improved catalytic activity. The spectroscopic investigations gave an evidence that the strong acid sites play an important role on controlling the catalytic activity. Among the catalysts investigated, the Pd-loaded sulfated zirconia catalyst with 1 wt% Pd was found to exhibit the highest catalytic activity in the presence of water vapor having the stability for 30 h of the reaction at $500^{\circ}C$. The successful performance of the catalyst might be attributed to promotional effect of Pd active sites and strong acid sites induced from surface sulfate species on zirconia.

• 공업화학
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• 제2권1호
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• pp.77-85
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• 1991

염산 및 불산으로 모더나이트를 처리하여 실리카/알루미나 비가 다른 일련의 시료를 만들었다. 이러한 시료에 대하여 암모니아 TPD와 피리딘 흡착으로 IR을 이용하여 산성도를 측정하고 o-xylene 반응의 활성과 이성화반응에 대한 선택성을 측정하였다. 그 결과 염산처리 시료는 실리카/알루미나 비가 증가할수록 구조알루미늄이 추출되어 산량이 감소하였으며 실리카/알루미나 비가 22인 시료가 다른 시료들보다 활성이 좋았다. 불산처리 시료는 불산처리 시 불소가 구조 중 규소원자와 결합하였으며 처리시간이 증가함에 따라 결합된 불소는 증가하였다. 이 경우의 활성은 염산처리와는 달리 알루미늄의 추출과 함께 모더나이트의 수산기가 불소로 치환되어 이로 인하여 산점이 줄어 활성이 감소하나 불산은 규소도 추출하므로 표면을 파고들어 새로운 면이 노출되어 산점이 형성되고 이 산점은 증가된 결합불소의 영향을 받아 강해지면서 활성이 다소 증가하였다.

• 공업화학
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• 제34권5호
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• pp.548-555
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• 2023

SAPO-34 catalysts were modified with polyethylene glycol (PEG) and Pb to improve their catalytic lifetime and selectivity for light olefins in the conversion of dimethyl ether to olefins (DTO). Hierarchical SAPO-34 catalysts and PbAPSO-34 catalysts were synthesized according to changes in the molecular weight of PEG (M.W. = 1000, 2000, 4000) and the molar ratio of Pb/Al (Pb/Al = 0.0015, 0.0025, 0.0035), respectively. By introducing PEG into the SAPO-34 catalyst crystals, an enhanced volume of mesopores and reduced acidity were observed, resulting in improved catalytic performance. Pb was successfully substituted into the SAPO-34 catalyst frameworks, and an increased BET surface area and concentration of acid sites in the PbAPSO-34 catalysts were observed. In particular, the concentrations of the weak acid sites, which induce a mild reaction, were increased compared with the concentrations of strong acid sites. Then, the P2000-Pb(25)APSO-34 catalyst was prepared by simultaneously utilizing the synthesis conditions for the P2000 SAPO-34 and Pb(25)APSO-34 catalysts. The P2000-Pb(25)APSO-34 catalyst showed the best catalytic lifetime (183 min based on DME conversion > 90%), with an approximately 62% improvement compared to that of the unmodified catalyst (113 min).

• Bulletin of the Korean Chemical Society
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• 제22권3호
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• pp.263-266
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• 2001

Isopropylation of phenol with 2-propanol has been carried out over Na-exchanged ZSM-5 zeolites to determine the effect of catalyst acidity on phenol conversion and product selectivity. The acid type and strength of the catalyst such as Lewis, weak and strong Bronsted acid sites are measured by pyridine adsorbed XPS and the catalytic properties are interpreted in terms of the acid properties. The active site and mechanism for the reaction are suggested based on evidence of study from the reactant adsorbed FT-IR.

• Bulletin of the Korean Chemical Society
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• 제16권6호
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• pp.507-511
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• 1995

Catalytic chlorination of chlorobenzene was studied in vapor phase using various solid-acid catalysts such as silica-alumina, alumina, zeolite and a modified clay prepared by impregnating bentonite with ferric chloride. The conversions of both chlorine gas and chlorobenzene showed high over silica-alumina, alumina and modified clay catalysts. However relatively large amounts of polychlorinated benzene derivatives were also observed. The active species of catalytic activity in chlorination of chlorobenzene in vapor phase were proved to be as Lewis acid sites by in-situ IR experiments. The strength of Lewis acid sites which were effective for the vapor-phase chlorination seemed to be having Hammett acidity Ho >-3.0. The selectivity to dichlorobenzenes was proved to be high over the zeolite catalyst due to their shape-selective properties. p-Dichlorobenzene or dichlorobenzene selectivities were improved more or less by changing the reaction conditions.

• Bulletin of the Korean Chemical Society
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• 제34권8호
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• pp.2399-2402
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• 2013

The catalytic pyrolysis of cellulose was carried out over SAPO-11 for the first time. Pyrolyzer-gas chromatography/mass spectroscopy was used for the in-situ analysis of the pyrolysis products. The acid sites of SAPO-11 converted most levoglucosan produced from the non-catalytic pyrolysis of cellulose to furans. In particular, the selectivity toward light furans, such as furfural, furan and 2-methyl furan, was high. When the catalyst/cellulose ratio was increased from 1/1 to 3/1 and 5/1, the increase in the quantity of acid sites led to the promotion of deoxygenation and the resultant increase of the contents of light furan compounds. Because furans can be used as basic feedstock materials, the augmentation of the economical value of bio-oil through the catalytic upgrading over SAPO-11 is considerable.

• 대한화학회지
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• 제56권5호
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• pp.563-570
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• 2012

Solid acid Mo(VI)/$ZrO_2$ with 2-10% Mo(VI) was coated on honeycomb monoliths by impregnation method. These catalytic materials were characterized by BET, $NH_3$-TPD/n-butylamine back titration, PXRD and SEM techniques. Phenyl salicylate (Salol) was synthesized via transesterification of methyl salicylate and phenol over these catalytic materials. An excellent yield (91.0%) of salol was obtained under specific reaction conditions. The effect of poisoning of acid sites of the catalytic material by adsorbing different bases and its effect on total surface acidity, powder XRD phases and catalytic activity was studied. A triangular correlation between the surface acidity, powder XRD phases and catalytic activity of Mo(VI)/$ZrO_2$ was observed. The thermally regenerated catalytic material was reused repeatedly with a consistent high yield of salol.

• 대한금속재료학회지
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• 제50권3호
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• pp.201-205
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• 2012

The effects of various manganese precursors for the low-temperature selective catalytic reduction (SCR) of $NO_x$ were investigated in terms of structural, morphological, and physico-chemical analyses. $MnO_x/TiO_2$ catalysts were prepared from three different precursors, manganese nitrate, manganese acetate(II), and manganese acetate(III), by the sol-gel method. The manganese acetate(III)-$MnO_x/TiO_2$ catalyst tended to suppress the phase transition from the anatase structure to the rutile or the brookite after calcination at $500^{\circ}C$ for 2 h. It also had a high specific surface area, which was caused by a smaller particle size and more uniform distribution than the others. The change of catalytic acid sites was confirmed by Raman and FT-IR spectroscopy and the manganese acetate(III)-$MnO_x/TiO_2$ had the strongest Lewis acid sites among them. The highest de-NOx efficiency and structural stability were achieved by using the manganese cetate(III) as a precursor, because of its high specific surface area, a large amount of anatase $TiO_2$, and the strong catalytic acidity.

• Bulletin of the Korean Chemical Society
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• 제28권10호
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• pp.1763-1770
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• 2007

Strong solid acid catalysts, NiO/Al2O3-TiO2/WO3 for ethylene dimerization were prepared by the addition of Al2O3 and the modification with WO3. The acid sites and acid strength were increased by the inductive effect of WO3 species bonded to the surface of catalysts. The larger the dispersed WO3 amount, the higher both the acidity and catalytic activity for ethylene dimerization. The addition of Al2O3 to TiO2 up to 5 mol% enhanced acidity and catalytic activity gradually due to the interaction between Al2O3 and TiO2 and consequent formation of Al-O-Ti bond.