• Applied Chemistry for Engineering
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• v.10 no.8
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• pp.1161-1168
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• 1999

The redox property of oxide materials of the 3rd period transition metals(Cr~Zn), V, Mo, and W was studied with temperature-programmed reduction/temperature-programmed oxidation(TPR/TPO) experiment. The peak temperatures of TPO spectra were equal to or lower than those of TPR spectra. And the peak shapes of TPO spectra were broader than those of TPR ones. The activation energies of TPR/TPO for the oxides of the 3rd period transition metals showed in the range of 33~149 kJ/mol, while for the oxides of V, Mo, and W, they showed relatively higher values. The change of activation energies of TPR/TPO with various metal oxides showed a similar trend to the change of their metal-oxygen bond strengths. The change of activation energies of o-xylene oxidation for various metal oxides was proportional to the difference (${\Delta}E_a$) between the activation energy of TPR and that of TPO. From these results, we concluded that the oxidation of o-xylene over various metal oxide catalysts follows the Mars-van Krevelen mechanism including the surface reduction-oxidation of the metal oxide itself.

• International Journal of Automotive Technology
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• v.7 no.3
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• pp.261-267
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• 2006

Understanding the mechanism of carbon oxidation is important for the successful modeling of diesel particulate filter regeneration. Carbon oxidation characteristics were investigated by temperature programmed oxidation(TPO) method as well as constant temperature oxidation(CTO) with a flow reactor including porous bed. The activation energy of carbon oxidation was increasing with temperature and had two different constant values in the early and the later stage of the oxidation process respectively in TPO experiment. Kinetic constants were derived and the reaction mechanisms were assumed from the experimental results and a simple reaction scheme was proposed, which approximately predicted the overall oxidation process in TPO as well as CTO.

• 한국신재생에너지학회:학술대회논문집
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• 2007.06a
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• pp.49-52
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• 2007

We investigated hydrogen storage and production properties using redox system of iron oxide($Fe_{3}O_{4}$ + $4H_{2}$ ${\leftrightarrows}$ 3Fe + $4H_{2}O$) modified with rhodium, ceria and zirconia under atmospheric pressure. Reduction of iron oxide with hydrogen(hydrogen storage) and re-oxidation of reduced iron oxide with steam(hydrogen evolution) was carried out using a temperature programmed reaction(TPR) technique. On the temperature programmed studies, the effects of amounts of cerium and zirconium on the re-oxidation rate of partial reduced iron oxides were increased with increasing metal additives amount, but the rhodium amount showed little effect on the re-oxidation rate. On the thermal studies, the re-oxidation rates were enhanced with increasing temperature(300 $^{\circ}C$ < 350 $^{\circ}C$).

• Bulletin of the Korean Chemical Society
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• v.20 no.12
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• pp.1457-1463
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• 1999

Structure and their redox property of the vanadium oxides prepared by decomposing NH₄VO₃ at various temperatures were studied by XRD, SEM, XPS, and temperature programmed reduction/temperature programmed oxidation (TPR/TPO) experiment. All TPR profiles have two sharp peaks in the temperature range 650-750℃, and the area ratio of the two sharp peaks changed from sample to sample. There were three redox steps in TPR/TPO profiles. The oxidation proceeded in the reverse order of the reduction process, and both the reactions proceeded via quite a stable intermediates. The changes of the morphological factor $(I_{(101)}/I_{(010)})$, the ratio of $O_{1S}$ peak area (O$_{1S}$( α)/O$_{1S}$( β)) in the XPS results, and the ratio of hydrogen consumption in TPR profiles with various vanadium oxides showed the distinct relationship between the structural property and their redox property of vanadium oxides. The change of the specific yield of phthalic anhydride with various vanadium oxides showed a very similar trend to those of the peak area ratio in TPR profiles, which meant that the first reduction step related to the partial oxidation of o-xylene on the vanadium oxide catalyst.

• Bulletin of the Korean Chemical Society
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• v.34 no.8
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• pp.2461-2465
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• 2013

Pd-$Ce/{\gamma}-Al_2O_3-TiO_2$ catalysts were prepared by combined sol-gel and impregnation methods. Transmission electron microscopy, X-ray diffraction, $H_2$-temperature-programmed reduction, $O_2$-temperature-programmed desorption, and ethanol oxidation experiments were conducted to determine the properties of the catalysts. Addition of an optimal amount of Ce improved the performance of the $Pd/{\gamma}-Al_2O_3-TiO_2$ catalyst in promoting the complete oxidation of ethanol. The catalyst with 1% Ce exhibited the highest activity, and catalyzed complete oxidation of ethanol at $175^{\circ}C$; its selectivity to $CO_2$ reached 87%. Characterization results show that addition of appropriate amount of Ce could enrich the PdO species, and weaken the Pd-O bonds, thus enhancing oxidation ability of the catalyst. Meanwhile, the introduction of $CeO_2$ could make PdO better dispersed on ${\gamma}-Al_2O_3-TiO_2$, which is beneficial for the improvement of the catalytic oxidation activity.

• Korean Chemical Engineering Research
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• v.44 no.2
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• pp.193-199
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• 2006

The catalytic oxidation of toluene over $-Al_2O_3$ supported copper-manganese oxide catalysts in the temperature range of $160-280^{\circ}C$ was investigated by employing a fixed bed flow reactor. The catalysts were characterized by BET, scanning electron microscopy (SEM), temperature-programmed reduction(TPR), temperature-programmed oxidation(TPO), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction(XRD) techniques. Catalytic oxidation of toluene was achieved at the below $280^{\circ}C$, and the optimal content of copper and manganese in the catalyst was found to be 15.0 wt％Cu-10.0 wt％Mn. From the TPR/TPO and XPS results, the redox peak of 15 Cu-10 Mn catalyst shifted to the lower temperature, and the binding energy was shifted to the higher binding energy. Furthermore, It is considered that $Cu_{1.5}Mn_{1.5}O_4$ is superior to Mn oxides and CuO in the role as active factor of catalysts from the XRD results and also catalytic activities are dependent on the redox ability and high oxidation state of catalysts.

• Clean Technology
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• v.2 no.1
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• pp.60-68
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• 1996

The oxidation of carbon monoxide of low concentration on the natural manganese dioxide (NMD) has been investigated in a fixed bed reactor. The experimental variables were concentration of oxygen (500ppm~99.8%) and carbon monoxide (500ppm~10000ppm) and catalyst temperature ($50{\sim}750^{\circ}C$). The NMD(Natural Manganese Dioxide) has been characterized by temperature - program reduction(TPR) using 2.4% $CO/H_2$ as a reducing agent, thermogravimetric analysis (TGA), and reduction of NMD by 2.4% $CO/H_2$. It was found that the NMD catalyst activity on the unit area was greater than the $MnO_2$ catalyst for oxidation of CO at the same temperature. The thermal stability of oxidation activity was considered to be maintained when the NMD was heated to $750^{\circ}C$. The TGA, reduction by CO, and TPR of the NMD showed that the NMD had active lattice oxygen which was easily liberated on heating in the absence and low concentration of oxygen. The reaction order in CO is 0.701 between 500~3500ppm and almost zero between 3500~10000ppm of CO.

• Transactions of the Korean Society of Automotive Engineers
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• v.19 no.3
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• pp.52-56
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• 2011

Active regeneration in CDPF requires $O_2$ which regenerates soot at high temperature. However, small amount of NO can interrupt $O_2$ regeneration in CDPF. To verify this phenomena, soot oxidation experiments using a flow reactor with a $Pr/CeO_2$ catalyst are carried out to simulate Catalyzed Diesel Particulate Filter (CDPF) phenomena. Catalytic soot oxidation with and without small amount of NO is conducted under tight contact condition. As the heating rate rises, the temperature gap of maximum reaction rate is increased between with and without 50ppm NO. To accelerate the $NO_2$ de-coupling effect, CTO process is performed to eliminate interfacial contact for that time. As CTO process is extended, temperature which indicates peak reaction rate increases. From this result, it is found that small amount of NO can affect tight contact soot oxidation by removal of interfacial contact between soot and catalyst.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.268-268
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• 2012

Adsorption and desorption of toluene from bare and $TiO_2$-coated silica with a mean pore size of 15 nm was studied using breakthrough curves and temperature programmed desorption. Thicknesses of $TiO_2$ films prepared by atomic layer deposition on silica were < 2 nm, and ~ 5 nm, respectively. For toluene adsorption, both dry and humid conditions were used. $TiO_2$-thin film significantly improved toluene adsorption capacity of silica under dry condition, whereas desorption of toluene from the surface as a consequence of displacement by water vapor was more pronounced for $TiO_2$-coated samples with respect to the result of bare ones. In the TPD experiments, silica with a thinner $TiO_2$ film (thickness < 2 nm) showed the highest reactivity for toluene oxidation to $CO_2$ in the absence and presence of water. We show that the toluene adsorption and oxidation reactivity of silica can be controlled by varying thickness of $TiO_2$ thin films.

• Korean Chemical Engineering Research
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• v.56 no.2
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• pp.281-290
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• 2018

As the internal combustion engine vehicles of high fuel efficiency and low emission are demanded, it becomes important to procure technologies for improving low-temperature performance of automotive catalyst systems. In this study, we showed that the combustion rate of diesel particulate matter is greatly enhanced at low temperature by applying fuel-borne catalyst and perovskite catalyst concurrently. It was tried to examine the correlation between elemental composition of perovskite catalyst and combustion activity of mixed catalyst system. To achieve this goal, we applied temperature-programmed oxidation technique in testing the combustion behavior of perovskite-mixed particulate matter bed which contained the element of fuel-borne catalyst or not. We tried to explain the synergetic action of two catalyst components by comparing the trends of concentrations of carbon dioxide and nitrogen oxide in temperature-programmed oxidation results.