• Applied Chemistry for Engineering
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• v.23 no.3
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• pp.253-258
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• 2012

The effects of active sites and valence states were investigated over $Pd/TiO_2$ catalyst on simultaneous oxidation of $CH_4$ and CO. The Pd species (PdO) crystallite size increased with increasing Pd loadings, which results in enhancement of the activity of $CH_4$ oxidation. Different results from the activity of $CH_4$ and CO oxidation were shown to be dependent on the Pd valence state on the surface of the catalyst prepared through a thermal treatment. XRD and $H_2-TPR$ analysis confirmed that $Pd^{2+}$species was predominated in the calcination catalyst, while $Pd^0$species was predominated in the reduction catalyst. Additionally, it could be found that the valence state of Pd was a more important factor on the catalytic activity than that of factors as the surface area and pore volume. The reaction mechanism of $CH_4$ and CO followed by the valence state of Pd could be identified using FT-IR analysis.

• Bulletin of the Korean Chemical Society
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• v.28 no.4
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• pp.529-532
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• 2007

Combined temperature programmed reaction (TPR) and infrared (IR) spectroscopic studies for Fischer- Tropsch reaction have been performed over Ru/SiO2 and Ru-Ag/SiO2 supported catalysts. Reaction of linearly absorbed CO with hydrogen starts at 375 K over Ru/SiO2 catalyst and reaches maximum at 420 K accompanied with an intensity decrease of linear CO absorption. The reaction with bridged absorbed CO peaks around 510-535 K. Addition of Ag yields mixed Ru-Ag bimetallic sites while it suppresses the formation of bridged bonded CO. Formation of methane on this modified surface occurs at 390 K and reaches maximum at 444 K. Suppression of hydrogen on the Ag-doped surface also occurs resulting in the formation of unsaturated hydrocarbons and of CHx intermediates not observed with Ru/SiO2 catalyst. Such intermediates are believed to be the building blocks of higher hydrocarbons during the Fischer-Tropsch synthesis. Linearly absorbed CO is found to be more reactive as compared to bridged CO. The Ag-modified surface also produces CO2 and carbon. On this surface, hydrogenation of CO begins at 390 K and reaches maximum at 494 K. The high temperature for hydrogenation of absorbed CO and C over Ru-Ag/SiO2 catalyst as compared to Ru/SiO2 catalyst is due to the formation of Ru-Ag bimetallic surfaces impeding hydrogen adsorption.

• Korean Chemical Engineering Research
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• v.46 no.5
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• pp.868-874
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• 2008

The Ni based adsorbent was prepared by co-precipitation method and its performance for removing carbon monoxide was investigated. Here, silica, aluminium silicate and ${\gamma}$-alumina were used for carriers of catalyst. $Ni(NO_3)_2{\cdot}6H_2O$ and $Ni(CH_3COO)_2{\cdot}4H_2O$ were utilized for Ni precursors. Precipitants were urea and citric acid. After precipitation of Ni salt on the carrier and following reduction using $H_2$ gas, adsorbent was prepared and its performance was analyzed based on EDS, TPR and XRD experiments. In accordance with change of precipitation agents, Ni salts on carrier, carriers and reduction condition. Adsorbent performance for removing carbon monoxide was investigated. The adsorbent with 54.8 wt% Ni prepared using urea precipitant under reduction condition at $500^{\circ}C$ for 3 h exhibited the best CO removal performance.

• Clean Technology
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• v.18 no.3
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• pp.259-264
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• 2012

Perovskite-type oxides were successfully prepared using malic acid method, characterized by TG/DTA, XRD, XPS, TEM and $H_2$-TPR and their catalytic activities for the combustion of benzene were determined. Almost of catalyst showed perovskite crystalline phase and 15-70 nm particle size. The $LaMnO_3$ catalysts showed the highest activity and the conversion reaches almost 100% at $350^{\circ}C$. The catalysts were modified to enhance the activity through substitution of metal into the A or B site of the perovskite oxides. In the $LaMnO_3$-type catalyst, the partial substitution of Sr into site the A-site enhanced the catalytic activity in the benzene combustion. In addition, the partial substitution of Co or Cu into site the B-site also enhanced the catalytic activity and the catalytic activity was in the order of Co > Cu > Fe in the $LaMn_{1-x}B_xO_3$ (B = Co, Fe, Cu) type catalyst.

• Transactions of the Korean hydrogen and new energy society
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• v.29 no.2
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• pp.170-180
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• 2018

After $MoS_2$ catalyst was prepared at 1, 30, and 70 atm, the hydrothermal pressure effect over preparation of $MoS_2$ was investigated in terms of catalyst characterization and direct methanation. Multifaceted characterization techniques such as XRD, BET, SEM, TPR, EDS, and XPS were used to analyze and investigate the effect of high pressure over the preparation of surface and bulk $MoS_2$ catalyst. Result from XRD, SEM, and BET demonstrated that $MoS_2$ was more dispersed as preparation pressure was increased, which resulted finer $MoS_2$ crystal size and higher surface area. EDS result confirmed that bulk composition was $MoS_2$ and XPS result showed that S/Mo mole ratio of surface was about 1.3. TPR showed that $MoS_2$ prepared at 30 atm possessed higher active surface sites than $MoS_2$ prepared at 1 atm and these sites could contribute to higher CO yield during methanation. Direct methanation was used to evaluate the CO conversion of the both catalysts prepared at 1 atm and 30 atm and reaction condition was at feed mole ratio of $H_2/CO=1$, GHSV=4800, 30 atm, temperature($^{\circ}C$) of 300, 350, 400, and 450. $MoS_2$ prepared at 30 atm showed more stable and higher CO conversion than $MoS_2$ prepared at 1 atm. Faster deactivation was occurred over $MoS_2$ prepared at 1 atm, which indicated that preparation pressure of $MoS_2$ catalyst was the dominant factor to improve the yield of direct methanation.

• Korean Chemical Engineering Research
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• v.55 no.1
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• pp.121-129
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• 2017

Pd based catalysts were prepared by impregnating palladium precursor using incipient wetness method on $TiO_2$, $Al_2O_3$, $ZrO_2$, and $SiO_2$ and were applied for the selective oxidation of $H_2$ in the presence of CO. Their physicochemical properties were studied by X-ray diffraction (XRD), $N_2$-sorption, temperature programmed desorption of CO (CO-TPD) and (CO+$H_2O$)-TPD, temperature programmed reduction of CO (CO-TPR) and XPS a. The results of CO- and (CO+$H_2O$)-TPD showed the correlation between peak temperature of TPD and catalytic activities for $H_2$ and CO conversion. The $Pd/ZrO_2$ catalyst exhibited the highest conversion of $H_2$. The addition of $H_2O$ vapor promotes the conversion of $H_2$ and CO by inducing easy desorption of CO and $H_2$ in the competitive adsorption of $H_2O$, CO and $H_2$.

• Clean Technology
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• v.28 no.1
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• pp.1-8
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• 2022

To confirm the applicability of the water gas shift reaction for the production of high purity hydrogen for petroleum cokes, an unutilized low grade resource, Cu/ZnO/MgO/Al₂O₃ (CZMA), catalyst was prepared using the co-precipitation method. The prepared catalyst was analyzed using BET and H₂-TPR. Catalyst reactivity tests were compared and analyzed in two cases: a single LTS reaction from syngas containing a high concentration of CO, and an LTS reaction immediately after the syngas passed through a HTS reaction without condensation of steam. Reaction characteristics in accordance with steam/CO ratio, flow rate, and temperature were confirmed under both conditions. When the converted low concentration of CO and steam were immediately injected into the LTS, the CO conversion was rather low in most conditions despite the presence of large amounts of steam. In addition, because the influence of the steam/CO ratio, temperature, and flow rate was significant, additional analysis was required to determine the optimal operating conditions. Meanwhile, carbon deposition or activity degradation of the catalyst did not appear under high CO concentration, and high CO conversion was exhibited in most cases. In conclusion, it was confirmed that when the Cu/ZnO/MgO/Al₂O₃ catalyst and the appropriate operating conditions were applied to the syngas composition containing a high concentration of CO, the high concentration of CO could be converted in sufficient amounts into CO₂ by applying a single LTS reaction.

• Clean Technology
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• v.25 no.4
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• pp.296-301
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• 2019

This study was conducted to investigate the characteristics of CO oxidation by NO poisoning in Pt/TiO₂ catalyst prepared by wet impregnation method and calcined at 400 ℃. In order to confirm the NO poisoning effect of the Pt/TiO₂ catalyst, the change of reaction activity was observed when NO was injected during the CO+O₂ reaction where it was ascertained that the CO conversion rate rapidly decreased below 200 ℃. Also, CO conversion was not observed below 125 ℃. Recovery of initial CO conversion was not verified even if NO injection was blocked at 125 ℃. Accordingly, various analyses were performed according to NO injection. First, as a result of the TPD analysis, it was confirmed that NO pre-adsorption in catalyst inhibited CO adsorption and conversion desorption from adsorbed CO to CO₂. When NO was pre-adsorbed, it was confirmed through H₂-TPR analysis that the oxygen mobility of the catalyst was reduced. In addition, it was validated through FT-IR analysis that the redox cycle (Pt²⁺→Pt⁰→Pt²⁺) of the catalyst was inhibited. Therefore, the presence of NO in the Pt/TiO₂ catalyst was considered to be a poisoning factor in the CO oxidation reaction, and it was determined that the oxygen mobility of the catalyst is required to prevent NO poisoning.

• Clean Technology
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• v.24 no.1
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• pp.35-40
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• 2018

$Co_3O_4$ catalysts for $N_2O$ decomposition were prepared by co-precipitation method. Ce and Zr were added during the preparation of the catalyst as promoter with the molar ratio (Ce or Zr) / Co = 0.05. Also, 1 wt% $K_2CO_3$ was doped to the prepared catalyst with impregnation method to investigate the effect of K on the catalyst performance. The prepared catalysts were characterized with SEM, BET, XRD, XPS and $H_2-TPR$. The $Co_3O_4$ catalyst exhibited a spinel crystal phase, and the addition of the promoter increased the specific surface area and reduced the particle and crystal size. It was confirmed that the doping of K improves the catalytic activity by increasing the concentration of $Co^{2+}$ in the catalyst which is an active site for catalytic reaction. The catalytic activity tests were carried out at a GHSV of $45,000h^{-1}$ and a temperature range of $250{\sim}375^{\circ}C$. The K-impregnated $Co_3O_4$ catalyst showed much higher activity than $Co_3O_4$ catalysts with promoter only. It is found that the K-impregnation increased the concentration of $Co^{2+}$ more than the added of promoter did, and lowered the reduction temperature to a great extent.

• Applied Chemistry for Engineering
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• v.22 no.5
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• pp.555-561
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• 2011

The objective of this study is the development of carbon recycle technology which converts $CO_2$ captured from flue gas to CO or carbon and reuse in industrial fields. Since $CO_2$ is very stable and difficult to decompose, metal oxide was used as an activation agent for the decomposition of $CO_2$ at low temperature. Metal oxides which convert $CO_2$ to CO or carbon at $500^{\circ}C$ were prepared using Zn-ferrite by the solid state reaction and hydrothermal synthesis. The behaviors of $CO_2$ decomposition were studied using temperature programmed reduction/oxidation (TPR/TPO) and thermogravimetric analyzer (TGA). Zn-ferrite containing 5 wt% ZnO showed the largest reduction and oxidation. Reduction by $H_2$ was 26.53 wt%, oxidation by $CO_2$ was 25.73 wt% and 96.98% of adsorbed $CO_2$ was decomposed to $CO_2$ and carbon with excellent oxidation-reduction behaviors.