• Journal of the Korean Chemical Society
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• v.56 no.1
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• pp.92-101
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• 2012

The degradation of one of the commercially important hydrogel based on acrylic acid and acryl amide, (acrylic acid-co-acryl amide) hydrogels, by means of ultrasound irradiation and its combination with heterogeneous ($TiO_2$) was investigated. 24 kHz of ultrasound irradiation was provided by a sonicator, while an ultraviolet source of 16 W was used for UV irradiation. The extent of sonolytic degradation increased with increasing ultrasound power (in the range 30-80 W). $TiO_2$ sonophotocatalysis led to complete (acrylic acid-co-acryl amide) hydrogels degradation with increasing catalyst loading, while, the presence of $TiO_2$ in the dark generally had little effect on degradation. Therefore, emphasis was totally on the sonolytic and sonophotocatalytic degradation of hydrogels and a synergy effect was calculated for combined degradation procedures (Ultrasound and Ultraviolet) in the presence of $TiO_2$ nanoparticles. $TiO_2$ sonophotocatalysis was always faster than the respective individual processes due to the enhanced formation of reactive radicals as well as the possible ultrasound-induced increase of the active surface area of the catalyst. A kinetics model based on viscosity data was used for estimation of degradation rate constants at different conditions and a negative order for the dependence of the reaction rate on total molar concentration of (acrylic acid-co-acryl amide) hydrogels solution within the degradation process was suggested.

• Korean Chemical Engineering Research
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• v.48 no.3
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• pp.332-336
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• 2010

Ionic liquid immobilized on mesoporous amorphous silica was prepared from the coupling of 1-(triethoxysilylpropyl)-3-n-alkyl-imidzolium halides with tetraethyl orthosilicate(TEOS) through template-free condensation under strong acidic conditions. The immobilized 1-n-butyl-3-methyl imidazolium bromide ionic liquid on amorphous silica(BMImBr-AS) was proved to be an effective heterogeneous catalyst for the synthesis of dimethyl carbonate(DMC) from transesterification of ethylene carbonate(EC) with methanol. High temperature, high carbon dioxide pressure and long reaction time were favorable for the reactivity of BMImBr-AS. Kinetic studies based on two step reactions revealed that the proposed reaction model fitted well the experimental data. The apparent activation energy was estimated to be 67.4 kJ/mol.

• Journal of Korean Society for Atmospheric Environment
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• v.19 no.E3
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• pp.121-127
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• 2003

The characteristics of heterogeneous photocatalytic decomposition were investigated at low concentration level of $O_3$on TiO$_2$for various operating parameters such as: loaded catalyst weight (0∼4 mg/$\textrm{cm}^2$), initial concentration of $O_3$(0.06∼10.0 ppm), gas flow rate (1.0 ∼ 2.5ι/min), and relative humidity (0∼80%). This study was conducted using a flow-type reactor at room temperature. Three kinds of pure TiO$_2$(P25, ST -01, and E- 23) were employed as photocatalyts. It was found that $O_3$removal ratio was identical, regardless of the loaded TiO$_2$weight in the range from 0.5 to 4.0 mg/$\textrm{cm}^2$. It was also found that higher initial ozone concentration results in greater oxidation rate of ozone and experimental data show kinetically a good agreement with Langmur-Hinshelwood kinetic model. We also observed that the removal ratio of $O_3$increases linearly with the increasing flow rate and also with the increasing relative humidity for each catalyst.

• Journal of the Korean Applied Science and Technology
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• v.25 no.1
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• pp.58-64
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• 2008

Pretreatment of eliminating FFA is needed to make biodiesel from animal fat recovered from leather wastes because its acid value is high. This study was carried out to investigate the influence of 4 different pretreatment methods, which are heterogeneous catalyst method, ion exchange resin method, low pressure.high temperature method, and alkali method on the eliminating FFA and fatty acid composition. The results showed that the rate of eliminating FFA increased in the order of alkali method > catalyst method > low pressure high temperature method > ion exchange method. In the case of pretreatment of alkali method using NaOH, the rate of eliminating FFA appeared more than 86% regardless of acid value. Therefore, it was considered that alkali method using NaOH was the most effective in the view of economical and productive aspects, taking it into account that the acid value of animal fat recovered from fleshing scrap generated during leather making processes was 7 to 8.

• Clean Technology
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• v.20 no.2
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• pp.116-122
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• 2014

Various types of MOFs (metal-organic frameworks) were prepared via hydrothermal and post-grafting methods and applied as catalysts for the synthesis of jasminaldehyde, one of the representative perfume intermediates, by Aldol condensation of benzaldehyde with heptanal. Although both acid and base sites could catalyze the reaction, the catalytic performance was strongly dependent on the physical properties as well as the nature of functionalization on MOFs. While the use of sulfonated MOF catalysts led to decrease of jasminaldehyde selectivity regardless of MOFs used, the selectivity change was found to rely on the MOF types in the case of the amine-functionalization. Among the catalysts tested, MIL-101 shows the best catalytic performance, which may suggest that MIL-101 has suitable acid properties to promote the Aldol condensation and the large pore of MIL-101 is also advantageous to alleviate the diffusion problem of bulky products.

• Tribology and Lubricants
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• v.35 no.2
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• pp.132-138
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• 2019

In this study, we demonstrate the effects of the acidic properties of montmorillonite (MMT), which is commonly used as a catalyst, on the conversion and selectivity of the dimer acid methyl ester (DAME) synthesis. We synthesize DAME by the dimerization of conjugated linoleic acid methyl ester (CLAME) and oleic acid methyl ester using MMT KSF. Incidentally, trimer acid methyl ester was formed as a by-product during the DAME synthesis. There is a necessity to adequately adjust the strength and quantity of the acid site to control the selectivity of DAME. Therefore, we vary the pH of the MMT acid by using various metal hydroxides. The purpose of this study is to increase the yield of monocyclic dimer acid methyl ester, which is a substance with adequate physical properties for industrial applications (e.g., lubricant and adhesive, etc.), using a heterogeneous catalyst. We report the dimerization of fatty acid methyl ester by using base treated-KSF, and apply it to conjugated soybean oil methyl ester. Then, we transmute the acid site properties of KSF, such as pH of 5 wt.% slurry KSF and various alkali metals (Li, Na, K, Ca). Characterization of base treated-KSF using a pH meter, x-ray diffraction, inductively coupled plasma-atomic emission spectrometer, Brunauer-Emmett-Teller surface analysis, and temperature-programmed desorption. We conduct an analysis of CLAME and DAME using nuclear magnetic resonance spectroscopy, gas chromatography, and gel permeation chromatography. Through these experiments, we demonstrate the effects of the acidic properties of KSF on the conversion and selectivity of the DAME synthesis, and evaluate its industrial potential by application to waste vegetable oil.

• 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.

• Korean Journal of Materials Research
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• v.32 no.2
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• pp.98-106
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• 2022

Metal-organic frameworks (MOFs) are widely used in various fields because they make it easy to control porous structures according to combinations of metal ions and organic linkers. In addition, ZIF (zeolitic imidazolate framework), a type of MOF, is made up of transition metal ions such as Co²⁺ or Zn²⁺ and linkers such as imidazole or imidazole derivatives. ZIF-67, composed of Co²⁺ and 2-methyl imidazole, exhibits both chemical stability and catalytic activity. Recently, due to increasing need for energy technology and carbon-neutral policies, catalysis applications have attracted tremendous research attention. Moreover, demand is increasing for material development in the electrocatalytic water splitting and metal-air battery fields; there is also a need for bifunctional catalysts capable of both oxidation/reduction reactions. This review summarizes recent progress of bifunctional catalysts for electrocatalytic water splitting and metal-air batteries using ZIF-67. In particular, the field is classified into areas of thermal decomposition, introduction of heterogeneous elements, and complex formation with carbon-based materials or polyacrylonitrile. This review also focuses on synthetic methods and performance evaluation.

• Clean Technology
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• v.29 no.2
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• pp.79-86
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• 2023

The homogeneous catalyst, Ru-MACHO-BH, selectively performs hydrogenation reactions only on the carbonyl group of α, β-unsaturated aldehyde compounds with extremely high reactivity and selectivity. However, the hydrogenation of α, β-unsaturated aldehydes involves a heterogeneous Diels-Alder reaction, resulting in the formation of significant amounts of byproducts, such as dimers. In this study, we used the Ru-MACHO-BH catalyst (Carbonyl hydrido (tetrahydroborato) [bis (2-diphenyl phosphino ethyl) amino] ruthenium(II)) to selectively hydrogenate the carbonyl group of a specific type of α, β-unsaturated aldehyde called methacryl aldehyde, leading to the synthesis of methallyl alcohol. Simultaneously, we applied diols to inhibit the formation of byproducts. The results demonstrate that monoethylene glycol can significantly reduce the formation of diols. Based on these results, we effectively suppressed the formation of dimers containing vinyl groups in methacryl aldehyde by using hydroquinone, which can efficiently inhibit the chemical interaction of vinyl groups. Consequently, the conversion rate of methacryl aldehyde was increased. Ultimately, by reducing the amount of the expensive homogeneous catalyst Ru-MACHO-BH to 1/10, we achieved a selectivity of over 90% and a yield of over 80% for the desired product, methallyl alcohol. These results provide a method to minimize yield reduction while reducing the usage of expensive catalysts, thereby improving cost-effectiveness. We expect that the reaction could be applied to various kinds of selective hydrogenation and has been successfully run on an industrial scale.

• Journal of the Korean Chemical Society
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• v.55 no.3
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• pp.430-435
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• 2011

Coal fly ash of thermal power plants converted into mesoporous materials MCM-41. The synthesized material was characterized by XRD, FT-IR, SEM, and EDS techniques. The catalytic activity of prepared material was studied for the synthesis of 5-arylindene malononitriles via Knoevenagel condensation of aromatic aldehydes and malonontrile is described. The features of present method are easy handling, stability, reusability, and eco-friendliness of catalyst, high yields, short reaction time, simple experimental and work up procedure.