• Korean Journal of Materials Research
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• v.32 no.3
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• pp.125-131
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• 2022

Effect of sulfation processes on the physicochemical properties of ZrO₂ and TiO₂ nanoparticles were thoroughly investigated. SO₄/ZrO₂ and SO₄/TiO₂ catalysts were synthesized to identify the acidity character of each. The wet impregnation method of ZrO₂ and TiO₂ nanoparticles was employed using H2SO₄ with various concentrations of 0.5, 0.75, and 1 M, followed by calcination at 400, 500, and 600 ℃ to obtain optimum conditions of the catalyst synthesis process. The highest total acidity was found when using 1 M SO₄/ZrO₂-500 and 1 M SO₄/TiO₂-500 catalysts, with total acidity values of 2.642 and 6.920 mmol/g, respectively. Sulfation increases titania particles via agglomeration. In contrast, sulfation did not practically change the size of zirconia particles. The sulfation process causes color of both catalyst particles to brighten due to the presence of sulfate. There was a decrease in surface area and pore volume of catalysts after sulfation; the materials' mesoporous structural properties were confirmed. The 1 M SO₄/ZrO₂ and 1 M SO₄/TiO₂ catalysts calcined at 500 ℃ are the best candidate heterogeneous acid catalysts synthesized in thus work.

• Bulletin of the Korean Chemical Society
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• v.28 no.11
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• pp.1951-1957
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• 2007

A new synthetic strategy based on the acid-base catalyzed sol-gel method was developed for the preparation of a series of mesoporous TiO2 nanoparticles. A key feature of the method involves a gradual change in pH (0.8- 9) during the sol-gel transition, which guarantees easy introduction of mesoporosity without relying on the well-established sonochemical or template approach. In addition, this method leads to the exclusive formation of the anatase phase stable enough to the calcination temperature up to 600 oC. The physicochemical properties of the particles in the series were characterized by various spectroscopic and analytical techniques such as wide-angle XRD, SAXRD, BET surface area, FE-SEM, TEM, FT-IR, TGA, and XPS. The photocatalytic efficiency of these materials was investigated for the oxidation of toluene under UV-irradiation. All but T-ad in the series exhibited high photocatalytic activity pushing the reaction into completion within 3 h. The reaction followed the first order kinetics, and the rate reaches as high as 3.9 × 10?2/min which exceeds the one with the commercially available Degussa P-25 by a factor of 3.2. When comparison is made among the catalysts, the reactivity increases with increase in the calcination temperature which in turn increases the crystallinity of the anatase phase, thus revealing the following rate orders: T-3 < T-4 < T-5 < T-6.

• Applied Chemistry for Engineering
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• v.25 no.1
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• pp.34-40
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• 2014

Mesoporous SAPO-34 catalyst was successfully synthesized by the hydrothermal method using carbon nanotube (CNT) as a secondary template. The effects of CNT contents (0.5, 1.5, 2.5, and 4.5 mol%) on catalytic performances were investigated. The synthesized catalysts were characterized with XRD, SEM, nitrogen physisorption isotherm and $NH_3$-TPD. Among the synthesized catalysts, SAPO-34 catalyst prepared by the addition of 1.5 mol% CNT (1.5C-SAPO-34) observed not only the largest amounts of mesopore volume but also acid sites. However, the mesopore volume was relatively decreased by further increasing of CNT contents due to the formation of small crystalline. The catalytic lifetime and the selectivity of light olefins ($C_2{\sim}C_4$) were examined for the dimethyl ether to olefins reaction. As a result, the 1.5C-SAPO-34 catalyst showed an improvement of ca. 36% in a catalytic lifetime and a better selectivity to light olefins as compared with the general SAPO-34 catalyst.

• Applied Chemistry for Engineering
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• v.21 no.3
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• pp.323-327
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• 2010

Ti-SBA-15 catalysts doped with lanthanide ion were synthesized using conventional hydrothermal method and they were characterized by XRD, FT-IR, DRS, $NH_3$-TPD and PL. We also examined the activity of these materials on the photocatalytic decomposition of methylene blue. La/Ti-SBA-15 samples with varying lanthanide ions doping maintained the mesoporous structure and the catalysts calcined at $500^{\circ}C$ for 6 h showed the highest crystallinity. With increasing the doping amount of lanthanide ion, the pore size and pore volume of La/Ti-SBA-15 materials decreased but the surface area increased. 1% La/Ti-SBA-15 catalysts showed the highest photocatalytic activity on the decomposition of methylene blue but the catalysts doped with more than 5% lanthanide ions showed lower activity compared to pure Ti-SBA-15 catalyst.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.77.2-77.2
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• 2013

In this talk, I will briefly review recent results of my group related to application of atomic layer deposition (ALD) for fabricating environmental catalysts and organic solar cells. ALD was used for preparing thin films of TiO2 and NiO on mesporous silica with a mean pore size of 15 nm. Upon depositing TiO2 thin films of TiO2 using ALD, the mesoporous structure of the silica substrate was preserved to some extent. We show that efficiency for removing toluene by adsorption and catalytic oxidation is dependent of mean thickness of TiO2 deposited on silica, i.e., fine tuning of the thickness of thin film using ALD can be beneficial for preparing high-performing adsorbents and oxidation catalysts of volatile organic compound. NiO/silica system prepared by ALD was used for catalysts of chemical conversion of CO2. Here, NiO nanoparticles are well dispersed on silica and confiend in the pore, showing high catalytic activity and stability at 800oC for CO2 reforming of methane reaction. We also used ALD for surface modulation of buffer layers of organic solar cell. TiO2 and ZnO thin films were deposited on wet-chemically prepared ZnO ripple structures, and thin films with mean thickness of ~2 nm showed highest power conversion efficiency of organic solar cell. Moreover, performance of ALD-prepared organic solar cells were shown to be more stable than those without ALD. Thin films of oxides deposited on ZnO ripple buffer layer could heal defect sites of ZnO, which can act as recombination center of electrons and holes.

• Korean Chemical Engineering Research
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• v.46 no.2
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• pp.279-285
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• 2008

The etherification of 2-naphthol with ethanol has been carried out over various solid acid catalysts. CNS, CNSWS, SCMS, MCF, and SBA-15 with and without sulfonic acid were used in this study as solid acid catalysts. The conversion of 2-naphthol and the selectivity of 2-naphthyl ethyl ether were obtained at reaction temperature = $180^{\circ}C$, $LHSV=1h^{-1}$, ethanol/2-naphthol molar ratio = 20 using a fixed-bed down flow reactor. The conversion of 2-naphthol and the selectivity of 2-naphthyl ethyl ether over silica group catalysts were higher than them over carbon group catalysts. The conversion of 2-naphthol was 70-90% and the selectivity of 2-naphthyl ethyl ether was more than 90% over silica group solid acid catalysts. It was performed XRD, SEM, TEM, and $NH_3-TPD$ to characterize solid acid catalysts.

• Bulletin of the Korean Chemical Society
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• v.35 no.11
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• pp.3205-3208
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• 2014

Catalytic gasification of cellulose was carried out in a U-type fixed reactor with Ni loaded MSU-F catalyst (Ni/MSU-F) and Ni loaded ${\gamma}-Al_2O_3$ (Ni/${\gamma}-Al_2O_3$). The characteristics of the catalysts were analyzed by using X-ray diffraction, $H_2$-temperature programmed reduction, and Brunauer-Emmett-Teller analyses. The operation conditions of catalytic gasification reactions were $750^{\circ}$ and 0.2 equivalence ratio. Air was used as gasification agent. Catalytic gasification characteristics, such as gas yield and gas composition ($H_2$, CO, $CO_2$, $C_1-C_4$), were measured and calculated. The gas yield of Ni/MSU-F was much higher than that of Ni/${\gamma}-Al_2O_3$. Especially high amount of hydrogen was produced by Ni/MSU-F.

• Korean Journal of Materials Research
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• v.22 no.10
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• pp.526-530
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• 2012

Silica-based ceramic-matrix composites have shown promise as advanced materials for many applications such as chemical catalysts, ceramics, pharmaceuticals, and electronics. $SiO_2$-CuO-$CeO_2$ multi-component powders and their thin film, using an oxalic acid template as a chelating agent, have larger surface areas and more uniform pore size distribution than those of inorganic acid catalysts. $SiO_2$-CuO-$CeO_2$ composite powders were synthesized using tetraethylorthosilicate, copper (II) nitrate hemi (pentahydrate), and cerium (III) nitrate hexahydrate with oxalic acid as template or pore-forming agent. The process of thermal evolution, the phase composition, and the surface morphology of these powders were monitored by thermogravimetry-differential thermal analysis (TG-DTA), X-ray diffractometry (XRD), field-emission scanning electron microscopy (FE-SEM), and energy dispersive X-ray spectrometry (EDXS). The mesoporous property of the powders was observed by Brunner-Emmett-Teller surface (BET) analysis. The improved surface area of this powder template with oxalic acid was $371.4m^2/g$. This multi-component thin film on stainless-steel was prepared by sol-gel dip coating with no cracks.

• Applied Chemistry for Engineering
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• v.10 no.7
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• pp.1020-1027
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• 1999

Heteropoly acid(HPW) catalysts supported on three different carriers, an amorphous silica, MCM-41 and MCM-48, with different loadings and calcination temperatures have been prepared and characterized by X-ray diffraction, nitrogen physorption, infrared spectroscopy, and $^{31}P$ magic angle spinning NMR. From the result of IR and NMR, it was shown that HPW retains the Keggin structure on the supported catalysts. No HPW crystal phase was developed even at HPW loadings as high as 35 wt % on the MCM-41 and 65 wt % MCM-48. Thus, HPW appeared to form finely dispersed species. In the hydrolysis reaction of di, bis, tri-pentaerythritol, HPW/MCM-41, 48 exhibited higher catalytic activity than $HPW/SiO_2$ or HPW.

• Korean Chemical Engineering Research
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• v.44 no.4
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• pp.417-423
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• 2006

A series of amine functionalized MCM-41 catalysts were prepared by aminopropyltrimethoxysilane grafting and their catalytic performance in Knoevenagel reaction of selected substrates was investigated. Water resistant and catalytically active amine grafted MCM-41 was prepared by post-synthetic silylation using methyltrimethoxysilane ; hydrogen bonding of the water molecules formed during the condensation reaction to the active N group was suppressed, which led to high TON of the reaction. Amine functionalized MCM-41 prepared by coating method produced high conversion, but the TON of the catalyst was much lower than that of the amine grafted MCM-41; pore volume of the functionalized MCM-41 decreased substantially and large portion of the immobilized amine is believed to be hydrogen bonded to each other, which can result in decrease in the basicity of the N group. A secondary amine group was prepared by room temperature condensation between aminopropylsilane and chloropropylsilane, and the MCM-41 grafted with the secondary amine group demonstrated the highest catalytic activity among the catalysts prepared.