• Clean Technology
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• v.18 no.1
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• pp.95-101
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• 2012

The Co and Ni catalysts supported on $Al_2O_3$ for partial oxidation of methane producing hydrogen were synthesized using impregnation to incipient wetness. And the promotion effects of metals such as Mg, Ce, La and Sr in partial oxidation of methane over these $Co/Al_2O_3$ and $Ni/Al_2O_3$ were investigated. Reaction activity of these catalysts for the partial oxidation of methane was investigated in the temperature range of 450~$650^{\circ}C$ at 1 atm and $CH_2/O_2$ = 2.0. The catalysts were characterized by BET, XRD and SEM/EDX. The results indicated that the catalytic performance of these catalysts was improved with the addition of 0.2 wt% metal promoter. The Mg promoted $Co/Al_2O_3$ catalyst showed the highest $CH_4$ conversion and hydrogen selectivity at higher temperature than $500^{\circ}C$. The Ce and Sr promoted Ni catalysts superior to Co-based catalysts in the low temperature range. The addition of metal promoter to $Co/Al_2O_3$ and $Ni/Al_2O_3$ catalysts increased the surface area.

• Clean Technology
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• v.28 no.4
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• pp.269-277
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• 2022

With the recent development of the biological enzymatic reaction industry, lactic acid (LA) can be mass-produced from biomass sources. In particular, a catalytic process that converts LA into acrylic acid (AA) is receiving much attention because AA is used widely in the petrochemical industry as a monomer for superabsorbent polymers (SAP) and as an adhesive for displays. In the LA conversion process, NaY zeolites have been previously shown to be a high-activity catalyst, which improves AA selectivity and long-term stability. However, NaY zeolites suffer from fast deactivation due to severe coking. Therefore, the aim of this study is to modify the acid-base properties of the NaY zeolite to address this shortcoming. First, base promoters, Ca ions, were introduced to the NaY zeolites to tune their acidity and basicity via ion exchange (IE) and incipient wetness impregnation (IWI). The IWI method showed superior catalyst selectivity and stability compared to the IE method, maintaining a high AA yield of approximately 40% during the 16 h reaction. Based on the NH₃- and CO₂-TPD results, the calcium salts that impregnated into the NaY zeolites were proposed to exit as an oxide form mainly at the exterior surface of NaY and act as additional base sites to promote the dehydration of LA to AA. The NaY zeolites were further treated with KOH before calcium impregnation to reduce the total acidity and improve the dispersion of calcium through the mesopores formed by KOH-induced desilication. However, this KOH treatment did not lead to enhanced AA selectivity. Finally, calcium loading was increased from 1wt% to 5wt% to maximize the amount of base sites. The increased basicity improved the AA selectivity substantially to 65% at 100% conversion while maintaining high activity during a 24 h reaction. Our results suggest that controlling the basicity of the catalyst is key to obtaining high AA selectivity and high catalyst stability.

• Journal of the Korean Electrochemical Society
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• v.23 no.2
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• pp.25-38
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• 2020

Photoelectrochemical water splitting has been considered as the most promising technology for generating hydrogen energy. Transition metal dichalcogenide (TMD) compounds have currently attracted tremendous attention due to their outstanding ability towards the catalytic water-splitting hydrogen evolution reaction (HER). Herein, we report the synthesis method of various transition metal dichalcogenide including MoS₂, MoSe₂, WS₂, and WSe₂ nanosheets as excellent catalysts for solar-driven photoelectrochemical (PEC) hydrogen evolution. Photocathodes were fabricated by growing the nanosheets directly onto Si nanowire (NW) arrays, with a thickness of 20 nm. The metal ion layers were formed by soaking the metal chloride ethanol solution and subsequent sulfurization or selenization produced the transition metal chalcogenide. They all exhibit excellent PEC performance in 0.5 M H₂SO₄; the photocurrent reaches to 20 mA cm^-2 (at 0 V vs. RHE) and the onset potential is 0.2 V under AM1.5 condition. The quantum efficiency of hydrogen generation is avg. 90%. The stability of MoS₂ and MoSe₂ is 90% for 3h, which is higher than that (80%) of WS₂ and WSe₂. Detailed structure analysis using X-ray photoelectron spectroscopy for before/after HER reveals that the Si-WS₂ and Si-WSe₂ experience more oxidation of Si NWs than Si-MoS₂ and Si-MoSe₂. This can be explained by the less protection of Si NW surface by their flake shape morphology. The high catalytic activity of TMDs should be the main cause of this enhanced PEC performance, promising efficient water-splitting Si-based PEC cells.

• Journal of Korean Society of Environmental Engineers
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• v.22 no.12
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• pp.2263-2273
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• 2000

Catalytic wet air oxidation of acetic acid over Mn-Ce based catalysts deposited on various supports ($SiO_2$, $TiO_2$, $ZrO_2$), $ZrSiO_4$, $ZrO_2(10wt%)/TiO_2$) have been carried out in high pressure microreactors. Also, promotional effects by small addition(O.5~1.0 wt%) of p-type semiconductors (CoO, $Ag_2O$, SnO) have been investigated. From the screening tests for initial activity ranking, both Mn(2.8)-Ce(7.2 wt%) and Ru(O.4)Mn(2.7)-Ce(6.9 wt%) supported on $TiO_2$ were selected as the promising reference candidates. In $Mn-Ce/TiO_2$ reference catalyst, addition of small amount of each p-type semiconductor (Co, Sn and Ag) resulted in activity promotional effect and the degree of the increase was in the following order: Co> Ag > Sn. Especially, $Mn-Ce/TiO_2$ promoted with 0.5 wt% Co gave the 2.6 folds activity increase compared to the reference case attributing to the surface area increase as well as synergy effect. In $Ru-Mn-Ce/TiO_2$ reference catalyst, only Co(1.0 wt%) promoted case showed a little reaction rate increase.

• Korean Chemical Engineering Research
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• v.48 no.3
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• pp.304-310
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• 2010

The FTS(Fischer-Tropsch synthesis) was carried out over precipitated iron-based catalysts with or without $SiO_2$ in a fixed-bed reactor at $250^{\circ}C$ and 1.5 MPa. The catalysts with $SiO_2$ showed much higher catalytic activity for the FTS than those without $SiO_2$, displaying excellent stability during 144 h of reaction. The X-ray diffraction and $N_2$ physisorption revealed that the catalysts with $SiO_2$ showed enhanced dispersion of $Fe_2O_3$ compared with those without $SiO_2$. Also, the results of temperature-programmed reduction by $H_2$ showed that the addition of $SiO_2$ markedly promoted the reduction of $Fe_2O_3$ into $Fe_3O_4$ and FeO at low temperatures below $260^{\circ}C$. In contrast, surface basicity of the catalysts, which was analyzed by temperature-programmed desorption of $CO_2$, decreased as a result of $SiO_2$ addition. We attribute the high and stable performance of the catalysts with $SiO_2$ to the improved dispersion and reducibility by the $SiO_2$ addition.

• Radiation Oncology Journal
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• v.17 no.4
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• pp.299-306
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• 1999

Purpose : The human genetic disorder ataxia-telangiectasia (AT) is a multisystem disease characterized by extreme radiosensitivity. The recent identification of the gene mutated in AT, ATM, and the demonstration that it encodes a homologous domain of phosphatidylinositol 3-kinase (PI3-K), the catalytic subunit of an enzyme involved in transmitting signals from the cell surface to the nucleus, provide support for a role of this gene in signal transduction. Although ionizing radiation was known to induce c-fos transcription, nothing is known about how ATM or PKCI mediated signal transduction pathway modulates the c-fos gene transcription and gene expression. Here we have studied the effect of PKCI on radiation sensitivity and c-fos transcription in normal and AT cells. Materials and Methods: Normal (LM217) and AT (AT5BIVA) cells were transfected with PKCI expression plasmid and the overexpression and integration of PKCI was evaluated by northern blotting and polymerase chain reaction, respectively. 5 Gy of radiation was exposed to LM and AT cells transfected with PKCI expression plasmid and cells were harvested 48 hours after radiation and investigated apoptosis with TUNEL method. The c-fos transcription activity was studied by performing CAT assay of reporter gene after transfection of c-fos CAT plasmid into AT and LM cells. Results: Our results demonstrate for the first time a role of PKCI on the radiation sensitivity and c-fos expression in LM and AT cells. PKCI increased radiation induced apoptosis in LM cells but reduced apoptosis in AT cells. The basal c-fos transcription activity is 70 times lower in AT cells than that in LM cells. The c-fos transcription activity was repressed by overexpression of PKCI in LM cells but not in AT cells. After induction of c-fos by Ras protein, overexpression of PKCI repressed c-fos transcription in LM cells but not in AT cells Conclusion: Overexpression of PKCI increased radiation sensitivity and repressed c-fos transcription in LM cells but not in AT cells. The results may be a. reason of increased radiation sensitivity of AT cells. PKCI may be involved in an ionizing radiation induced signal transduction pathway responsible for radiation sensitivity and c-fos transcription. The data also provided evidence for novel transcriptional difference between LM and AT cells.

• Applied Chemistry for Engineering
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• v.21 no.6
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• pp.648-652
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• 2010

Catalytic activities of the partial oxidation of methane (POM) to hydrogen were investigated over Pd(5)/Ti-SPK and Pd(5)/Zr-SPK in a fixed bed flow reactor (FBFR) under atmosphere, and the catalysts were characterized by BET, XPS, XRD. The BET surface areas, pore volume and pore width of Horvath-Kawaze, micro pore area and volume of t-plot of Pd(5)/Ti-SPK and Pd(5)/Zr-SPK were $284m^2/g$, $0.233cm^3/g$, 3.9 nm, $30m^2/g$, $0.015cm^3/g$ and $396m^2/g$, $0.324cm^3/g$, 3.7nm, $119m^2/g$, $0.055cm^3/g$, repectively. The nitrogen adsorption isotherms were type IV with hysteresis. XPS showed that Si 2p and O 1s core electronlevels of Ti-SPK and Zr-SPK substituted Ti and Zr shifted to slightly lower binding energies than SPK. The oxidation states of Pd on the surface of catalysts were $Pd^0$ and $Pd^{+2}$. XRD patterns showed that crystal structures of fresh catalyst changed amorphous into crystal phase after reaction. The conversion and selectivity of POM to hydrogen over Pd(5)/Ti-SPK and Pd(5)/Zr-SPK were 77, 84% and 78, 72%, respectively, at 973 K, $CH_4/O_2$ = 2, GHSV = $8.4{\times}10^4mL/g_{cat}{\cdot}h$ and were kept constant even after 3 days in stream. These results confirm superior activity, thermal stability, and physicochemical properties of catalyst in POM to hydrogen.

• Journal of the Korean Institute of Gas
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• v.27 no.3
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• pp.19-26
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• 2023

Hydrogen, a clean energy source free of COx emissions, is poised to replace fossil fuels, with its usage on the rise. Despite its high energy content per unit mass, hydrogen faces limitations in storage and transportation due to its low storage density and challenges in long-term storage. In contrast, ammonia offers a high storage capacity per unit volume and is relatively easy to liquefy, making it an attractive option for storing and transporting large volumes of hydrogen. While NH₃ decomposition is an endothermic reaction, achieving excellent low-temperature catalytic activity is essential for process efficiency and cost-effectiveness. The study examined the effects of different zeolite types (5A, NaY, ZSM5) on NH₃ decomposition activity, considering differences in pore structure, cations, and Si/Al-ratio. Notably, the 5A zeolite facilitated the high dispersion of Ni across the surface, inside pores, and within the structure. Its low Si/Al ratio contributed to abundant acidity, enhancing ammonia adsorption. Additionally, the presence of Na and Ca cations in the support created medium basic sites that improved N₂ desorption rates. As a result, among the prepared catalysts, the 15 wt%Ni/5A catalyst exhibited the highest NH₃ conversion and a high H₂ formation rate of 23.5 mmol/g_cat·min (30,000 mL/g_cat·h, 600 ℃). This performance was attributed to the strong metal-support interaction and the enhancement of N₂ desorption rates through the presence of medium basic sites.