• Korean Chemical Engineering Research
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• v.60 no.4
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• pp.620-629
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• 2022

By varying various experimental conditions such as heating rate, molar hourly space velocity (MHSV), and nitridation reaction temperature, vanadium oxynitride was prepared through temperature programmed reduction/nitridation reaction (TPRN) of vanadium pentoxide and ammonia, and characterization were performed. In order to investigate the physico-chemical properties of the prepared catalyst, N₂ adsorption-desorption analysis, X-ray diffraction analysis (XRD), hydrogen temperature programmed reduction (H₂-TPR), temperature programmed oxidation (TPO), ammonia temperature programmed desorption (NH₃-TPD), transmission electron microscopy (TEM) was performed. Transformation of V₂O₅ with 5 m² g^-1 low specific surface area by reduction at 340 ℃ to V₂O₃ showed a high specific surface area value of 115 m² g^-1 by micropore formation. As the nitridation temperature increased beyond that, the specific surface area continued to decrease due to sintering. The nitridation reaction variable that had the greatest influence on the specific surface area was the reaction temperature, and the x + y value of VN_xO_y of a single phase approached from 1.5 to 1.0 as the nitridation reaction temperature increased. At a high reaction temperature of 680 ℃, the cubic lattice constant a was VN. close to the value. At 680 ℃, the highest nitridation temperature among the experimental conditions, the ammonia conversion rate was 93%, and no deactivation was observed.

• Bulletin of the Korean Chemical Society
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• v.34 no.12
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• pp.3635-3640
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• 2013

We prepared Ni and Pd-modified $TiO_2@SiO_2$ core-shell nanostructures and then analyzed them by scanning electron microscopy, optical microscopy, X-ray diffraction crystallography, FT-IR and UV-Visible absorption spectroscopy. In addition, their CO oxidation performance was tested by temperature-programmed mass spectrometry. The CO oxidation activity showed an order of Ni-$TiO_2@SiO_2$ ($900^{\circ}C$) < Ni-$TiO_2@SiO_2$ ($90^{\circ}C$) < Ni-$TiO_2@SiO_2$ ($450^{\circ}C$) in the first CO oxidation run, and greatly improved activity in the same order in the second run. The $T_{10%}$ (the temperature at 10% CO conversion) corresponds to the CO oxidation rate of $2.8{\times}10^{-5}$ molCO $g{_{cat}}^{-1}s^{-1}$. For Ni-$TiO_2@SiO_2$ ($450^{\circ}C$), the $T_{10%}$ was observed at $365^{\circ}C$ in the first run and at $335^{\circ}C$ in the second run. For the Pd-$TiO_2@SiO_2$ ($450^{\circ}C$), the $T_{10%}$ was observed at a much lower temperature of $263^{\circ}C$ in the first CO oxidation run, and at $247^{\circ}C$ in the second run. The CO oxidation activities of transition metal modified $TiO_2@SiO_2$ core-shell nanostructures presented herein provide new insights that will be useful in developing catalysts for various environments.

• Applied Chemistry for Engineering
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• v.17 no.5
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• pp.490-497
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• 2006

$V_{2}O_{5}$/$TiO_{2}$ catalyst can be deactivated by ammonium salts formed by $SO_{2}$ oxidation and unreacted ammonium in presence of $SO_{2}$ in flue gas. The deactivation of catalyst by $SO_{2}$ depends on the $SO_{2}$ oxidation to $SO_{3}$. The oxidation of $SO_{2}$ is weakly affected by oxygen concentration, and strongly by the amount of vanadium loaded onto titania supports. Because unreacted ammonia is one of elements to form the ammonium salts, it is important to control the mole ratio of $NH_{3}/NOx$ in SCR. Thus the experiments about $NH_{3}/NOx$ were carried out. The reason of low activity of catalyst deactivated by ammonium salts is the change of pore volume. And TPD (Temperature Programmed Decomposition) was performed to find the decomposition of ammonium bisulfate on deactivated catalyst.

• Clean Technology
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• v.17 no.1
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• pp.41-47
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• 2011

[ $MnO_2$ ]catalysts were prepared by precipitation method using potassium manganate and manganese acetate. The effect of calcination temperatures of $MnO_2$ catalysts for CO oxidation has been studied and their physicochemical properties were studied by X-ray diffraction (XRD), $N_2$ sorption, temperature programmed reduction of $H_2$ ($H_2-TPR$), and temperature programmed desorption of CO (CO-TPD) techniques. $MnO_2$ calcined at $300^{\circ}C$ catalyst has a large surface area $181m^2/g$ having a narrow pore size distribution at 9 nm. The results of XRD and $H_2-TPR$ showed that the catalysts calcined at different temperatures showed mixed oxidation states of Mn such as $Mn^{4+}$ and $Mn^{3+}$. CO-TPD showed that the quantity of $CO_2$ desorbed was decreased with increasing the calcination temperatures. The catalytic activity over the catalyst calcined at $300^{\circ}C$ exhibited the highest conversion reaching to 100% at $200^{\circ}C$. $H_2O$ vapor showed an inhibiting effect on the efficiency of the catalyst because of co-adsorption with CO on the active sites of manganese oxide catalysts and the initial catalytic activity of CO oxidation could be regenerated by removing $H_2O$ vapor in the reactants.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.663-663
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• 2013

We prepared Cu oxides, and Ni and Pd-TiO2@SiO2 core-shellnanostructures, and tested their CO oxidation performances by temperature-programmed mass spectrometry. We found the starting temperatures of CO oxidation are around $200^{\circ}C$ and $300^{\circ}C$ for Ni and Pd-TiO2@SiO2 nanostructures, respectively. Cu oxides are cubes with 50~200 nm with, prepared with different concentrations of NaOH and ascorbic acid. For the core-shell structures, we prepared 100 nm SiO2 spheres, first coated the surface with TiO2 precursor, and then coated with Ni and Pd. Their characteristics are further examined by scanning electron microscopy, optical microscope, FT-IR, and UV-Vis absorption spectroscopy.

• Applied Chemistry for Engineering
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• v.17 no.5
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• pp.451-457
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• 2006

We synthesized phase pure CrN having surface areas up to $47m^2/g$ starting from $CrCl_{3}$ with $NH_{3}$. Thermal Gravimetric Analysis coupled with X-ray diffraction was carried out to identify solid state transition temperatures and the phase after each transition. In addition, the BET surface areas, pore size distributions, and crystalline diameters for the synthesized materials were analyzed. Space velocity influenced a little to the surface areas of the prepared materials, while heating rate did not. We believe it is due to the fast removal of reaction by-products from the system. Temperature programmed reduction results revealed that the CrN was hardly passivated by 1% $O_{2}$. Molecular nitrogen was detected from CrN at 700 and $950^{\circ}C$, which may be from lattice nitrogen. In temperature programmed oxidation with heating rate of 10 K/min in flowing air, oxidation started at or higher than $300^{\circ}C$ and resulting $Cr_{2}O_{3}$ phase was observed with XRD at around $800^{\circ}C$. However the oxidation was not completed even at $900^{\circ}C$. CrN catalysts were highly active for n-butane dehydrogenation reaction. Their activity is even higher than that of a commercial $Pt-Sn/Al_{2}O_{3}$ dehydrogenation catalyst in terms of volumetric reaction rate. However, CrN was not active in pyridine hydrodenitrogenation.

• Bulletin of the Korean Chemical Society
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• v.31 no.11
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• pp.3283-3290
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• 2010

The gas-phase dehydration of glycerol to acrolein was carried out over 10 wt % HSiW catalysts supported on different supports, viz. $\gamma-Al_2O_3$, $SiO_2-Al_2O_3$, $TiO_2$, $ZrO_2$, $SiO_2$, AC, $CeO_2$ and MgO. The same reaction was also conducted over each support without HSiW for comparison. Several characterization techniques, $N_2$-physisorption, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), the temperature-programmed desorption of ammonia ($NH_3$-TPD), temperature-programmed oxidation (TPO) with mass spectroscopy and CHNS analysis were employed to characterize the catalysts. The glycerol conversion generally increased with increasing amount of acid sites. Ceria showed the highest 1-hydroxyacetone selectivity at $315^{\circ}C$ among the various metal oxides. The supported HSiW catalyst showed superior catalytic activity to that of the corresponding support. Among the supported HSiW catalysts, HSiW/$ZrO_2$ and HSiW/$SiO_2-Al_2O_3$ showed the highest acrolein selectivity. In the case of HSiW/$ZrO_2$, the initial catalytic activity was recovered after the removal of the accumulated carbon species at $550^{\circ}C$ in the presence of oxygen.

• 한국신재생에너지학회:학술대회논문집
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• 2008.05a
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• pp.487-490
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• 2008

Temperature programmed oxidation (TPO) is used to characterize coke species deposited on commercial nickel catalyst, C11-PR during propane pre-reforming. Propane pre-reforming performed under various condition, S/C from 1.5 to 2.5 and temperature from $350^{\circ}C$ to $450^{\circ}C$. There are three kinds of coke species detected by TPO: (i) reactive coke, (ii) coke deposited on metal site and (iii) coke deposited on acid support. Coke deposited on metal and support are minimized although reactive coke is generated at temperature of $400^{\circ}C$ and S/C of 2.0. Reactive coke is expected to remove easily below temperature of $200^{\circ}C$. Therefore, optimized pre-reforming condition for propane is $400^{\circ}C$ and S/C of 2.0.

• Bulletin of the Korean Chemical Society
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• v.26 no.2
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• pp.281-284
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• 2005

The Fe/MgO catalysts with different Fe loadings (1, 4, 6, 15 and 30 wt% Fe) were prepared by a wet impregnation with iron nitrate as precursor. All of the catalysts were characterized by BET surface analyzer, X-ray diffraction (XRD), temperature-programmed reduction (TPR), and X-ray photoelectron spectroscopy (XPS). The maximum removal capacity of $H_2S$ was obtained with 15 wt% Fe/MgO catalyst which had the highest BET surface area among the measured catalysts. XRD of Fe/MgO catalysts showed that well dispersed Fe particles could be present on Fe/MgO with Fe loadings below 15 wt%. The crystallites of bulk $\alpha$-$Fe_2O_3$ became evident on 30 wt% Fe/MgO, which were confirmed by XRD. TPR profiles showed that the reducibility of Fe/MgO was strongly related to the loaded amounts of Fe on MgO support. Therefore, the highest removal efficiency of $H_2S$ in wet oxidation could be ascribed to a good dispersion and high reducibility of Fe/MgO catalyst. XPS studies indicated that the $H_2S$ oxidation with Fe/MgO could proceed via the redox mechanism ($Fe^{3+}\;{\leftrightarrow}\;Fe^{2+}$).

• Journal of Hydrogen and New Energy
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• v.17 no.1
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• pp.21-30
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• 2006

[ $M/Fe_2O_3$ ] (M=Rh, Ce and Zr) mixed oxides were prepared using urea method to develop a medium for chemical hydrogen storage by their redox cycles. And their redox behaviors by repeated cycles were studied using temperature programmed reaction(TPR) technique. Additives such as Rh, Ce and Zr were added to iron oxides in order to lower the reaction temperature for reduction by hydrogen and re-oxidation by water-splitting. From the results, concentration of urea used as a precipitant had little effect on particle size and reduction property of iron oxide. TPR patterns of iron oxide consisted of two reduction peaks due to the course of $Fe_2O_3\;{\rightarrow}\;Fe_3O_4\;{\rightarrow}\;Fe$. The results of repeated redox tests showed that Rh added to iron oxide have an effect on lowering the re-oxidation temperature by water-splitting. Meanwhile, Ce and Zr additives played an important role in prevention of deactivation by repeated cycles. Finally, Fe-oxide(Rh, Ce, Zr) sample added with Rh, Ce and Zr showed the lowest re-oxidation temperature by water-splitting and maintained high $H_2$ recovery in spite of the repeated redox cycles. Consequently, it is expected that Fe-oxide(Rh, Ce, Zr) sample can be a feasible medium for chemical hydrogen storage using redox cycle of iron oxide.