• Clean Technology
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• v.13 no.1 s.36
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• pp.54-63
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• 2007

Even traces of CO in the hydrogen-rich feed gas to proton exchange membrane fuel cells (PEMFC) poison the platinum anode electrode and dramatically decrease the power output. In this work, a variety of catalytic materials consisting of $Cu/Ce_xZr_{1-x}O_2$, (x = 0.0-1.0) were synthesised, characterized and tested for CO oxidation and preferential oxidation of CO (PROX). These catalysts prepared by hydrothermal and deposition-precipitation methods. The catalysts were characterized by XRD, XRF, SEM, BET, $N_2O$ titration and oxygen storage capacity (OSC) measurement. The effects of composition of the support and degree of excess oxygen were investigated fur activity and $CO_2$ selectivity with different temperatures. The composition of the support markedly influenced the PROX activity. Among the various $Cu/Ce_xZr_{1-x}O_2$ catalysts having different composition, $Cu/Ce_{0.9}Zr_{0.1}O_2$ and $Cu/Ce_{0.7}Zr_{0.3}O_2$ showed the highest activities (>99%) and selectivities (ca.50%) in the temperature range of $150{\sim}160^{\circ}C$. It was found that by using of $Ce_xZr_{1-x}O_2$ mixed oxide support which possesses a high oxygen storage capacity, oxidation-reduction activity of Cu-based catalyst was improved, which resulted in the increase of catalytic activity and selectivity of CO oxidation in excess $H_2$ environments.

• Journal of Hydrogen and New Energy
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• v.14 no.2
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• pp.155-170
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• 2003

$Cu-Ce/{\gamma}-Al_2O_3$ based catalysts were prepared and tested for selective oxidation of CO in a $H_2$-rich stream(1% CO, 1% $O_2$, 60% $H_2$, $N_2$ as balance). The effects of Cu loading and weight ratio(=Cu/(Cu+Ce)) upon both activity and selectivity were investigated upon the change in temperatures, It was also examined how the activity and selectivity of catalysts were varied with the presence of $CO_2$ and $H_2O$ in the reactant feed. Among the various Cu-Ce catalysts with different catalytic metal composition, Cu-Ce(4 : 16 wf%) /${\gamma}-Al_2O_3$ catalyst showed the highest activity(>$T_{99}$) and selectivities(50-80%) under wide range of temperatures($175-220^{\circ}C$). However, in the Cu-Ce(4 : 16 wt%)/ ${\gamma}-Al_2O_3$, the presence of $CO_2$ and $H_2O$ in the reactant feed decreased the activity and the maximum activity(>$T_{99}$) in terms of reaction temperature moved by about $25^{\circ}C$ toward higher temperature, the $T_{>99}$ window was seen between $210-230^{\circ}C$ (selectivity 50-75%). From $CO_2-/H_2O-TPD$, it can be concluded that the main cause for the decrease in catalytic activity may be attributed to the blockage of the active sites by competitive adsorption of water vapor and $CO_2$ with the reactant at low temperatures.

• Journal of Hydrogen and New Energy
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• v.30 no.3
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• pp.209-219
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• 2019

Methanol is a liquid fuel which could also be produced from renewable energy sources and has appreciably high energy density. In this work, we investigated the application of $Ce_{0.9}Gd_{0.1}O_{2-x}$ supported Cu and Ni catalysts for hydrogen production via methanol steam reforming. Catalysts were synthesized by solution combustion synthesis. The prepared catalysts with various active materials and Cu loading amounts were tested in a reactor at $200-300^{\circ}C$, 0-5 barg range and steam to methanol molar ratio was 1.5. The catalytic properties of Cu and Ni were compared, and the catalytic performance was shown to depend on the amounts of metal loading and operating conditions such as reaction temperature and pressure.

• Journal of Hydrogen and New Energy
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• v.28 no.1
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• pp.1-8
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• 2017

Cu/Mn/Ce catalysts for water gas shift (WGS) reaction were synthesized by urea-nitrate combustion method with the fixed molar ratio of Cu/Mn as 1:4 and 1:1 with the doping concentration of Ce from 0.3 to 0.8 mol%. The prepared catalysts were characterized with SEM, BET, XRD, XPS, $H_2$-TPR, $CO_2$ TPD, $N_2O$ chemisorption analysis. The catalytic activity tests were carried out at a GHSV of $28,000h^{-1}$ and a temperature range of 200 to $400^{\circ}C$. The Cu/Mn(CM) catalysts formed Cu-Mn mixed oxide of spinel structure ($Cu_{1.5}Mn_{1.5}O_4$) and manganese oxides ($MnO_x$). However, when a small amount of Ce was doped, the growth of $Cu_{1.5}Mn_{1.5}O_4$ was inhibited and the degree of Cu dispersion were increased. Also, the doping of Ce on the CM catalyst reduced the reduction temperature and the base site to induce the active site of the catalyst to be exposed on the catalyst surface. From the XPS analysis, it was confirmed that maintaining the oxidation state of Cu appropriately was a main factor in the WGS reaction. Consequently, Ce as support and dopant in the water gas shift reaction catalysts exhibited the enhanced catalytic activities on CM catalysts. We found that proper amount of Ce by preparing catalysts with different Cu/Mn ratios.

• Journal of Hydrogen and New Energy
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• v.25 no.3
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• pp.227-233
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• 2014

Simulated waste-derived synthesis gas has been tested for hydrogen production through water-gas shift (WGS) reaction over supported Cu catalysts prepared by co-precipitation method. $CeO_2$, $ZrO_2$, MgO, and $Al_2O_3$ were employed as supports for WGS reaction in this study. $Cu-CeO_2$ catalyst exhibited excellent catalytic activity as well as 100% $CO_2$ selectivity for WGS in severe conditions ($GHSV=40,206h^{-1}$ and CO concentration = 38.0%). In addition, $Cu-CeO_2$ catalyst showed stable CO conversion for 20h without detectable catalyst deactivation. The high activity and stability of $Cu-CeO_2$ catalyst are correlated to its easier reducibility, high oxygen mobility/storage capacity of $CeO_2$.

• Journal of Hydrogen and New Energy
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• v.32 no.6
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• pp.455-463
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• 2021

In this study, CeO₂ support is synthesized from cerium hydroxy carbonate prepared using precipitation/digestion method using KOH and K₂CO₃ as the precipitants. The Cu was impregnated to CeO₂ support with the different loading (Cu loading=10-40 wt. %). The prepared Cu/CeO₂ catalysts were applied to a single stage water gas shift (WGS) reaction. Among the prepared catalysts, the 20Cu/CeO₂ catalyst contained 20 wt.% of Cu showed the highest CO conversion (Xco=68% at 400℃). This result was mainly due to a large amount of active sites. In addition, the activity of the 20 Cu/CeO₂ catalyst was maintained without being deactivated for 100 hours because of the strong interaction between Cu and CeO₂. Therefore, it was confirmed that 20 Cu/CeO₂ is a suitable catalyst for a single WGS reaction.

• Journal of Hydrogen and New Energy
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• v.28 no.4
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• pp.345-351
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• 2017

Single stage water-gas shift reaction has been carried out at a gas hourly space velocity of $150,494h^{-1}$ over $Cu-Ce_{0.8}Zr_{0.2}O_2$ catalysts prepared by a co-precipitation method. Cu loading was optimized to obtain highly active co-precipitated $Cu-Ce_{0.8}Zr_{0.2}O_2$ catalysts for single stage water-gas shift reaction. 80 wt.% $Cu-Ce_{0.8}Zr_{0.2}O_2$ exhibited the excellent catalytic performance as well as 100% $CO_2$ selectivity (CO conversion = 27% at $240^{\circ}C$ for 50 h). The high activity and stability of 80 wt.% $Cu-Ce_{0.8}Zr_{0.2}O_2$ are correlated to low activation energy and large amount of surface Cu atoms.

• Journal of Hydrogen and New Energy
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• v.18 no.1
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• pp.32-39
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• 2007

CO oxidation and selective CO oxidation of $La_xCe_{1-x}Co_yCu_{1-y}O_{3-{\alpha}}$ perovskite(x=1, 0.9, 0.7. 0.5; y=1, 0.9, 0.7, 0.5) were investigated. For CO oxidation, catalytic activities were studied according to different preparation conditions such as pH and calcination temperature. The influence of the change of the $O_2$ concentration for selective CO oxidation was studied, too. The substitution of Ce for La improved the catalytic activity for CO oxidation and selective CO oxidation and best activity was observed for $La_{0.7}Ce_{0.3}CoO_3$ prepared at pH 11 and calcined at $600^{\circ}C$. The temperature of 90% CO conversion for CO oxidation using $La_{0.7}Ce_{0.3}CoO_3$ was $230^{\circ}C$. In contrast to the enhancement effect by Ce substitution, the partial substitution of Cu for Co in $LaCo_yCu_{1-y}O_{3-{\alpha}}$ decreased catalytic activities for CO oxidation reaction compared to that using $LaCoO_3$. For selective CO oxidation, the best CO conversion was 66% at $230^{\circ}C$ for $La_{0.7}Ce_{0.3}CoO_3$. The CO conversion of $La_{0.7}Ce_{0.3}CoO_3$ was greatly increased from 66% to 91% as increasing $O_2$ concentration from 1% to 2%.

• Journal of Hydrogen and New Energy
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• v.18 no.2
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• pp.116-123
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• 2007

[ $La_{0.5}Ce_{0.5}Co_{1-x}Cu_xO_{3-{\alpha}}$ ](X=0, 0.1, 0.3, 0.5) perovskites were prepared by coprecipitation method at pH 7 or pH 11 and its catalytic activity of selective CO oxidation was investigated. The characteristics of these catalysts were analyzed by $N_2$ adsorption, X-ray diffraction(XRD), SEM, $O_2$-temperature programmed desorption(TPD). The pH value at a preparation step made effect on particle morphology. The smaller particle was obtained with a condition of pH 7. The better catalytic activity was observed using catalysts prepared at pH 7 than pH 11. The maximum CO conversion of 98% was observed over $La_{0.5}Ce_{0.5}Co_{0.7}Cu_{0.3}O_{3-{\alpha}}$ at $320^{\circ}C$. Below $200^{\circ}C$, the most active catalyst was $La_{0.5}Ce_{0.5}Co_{0.9}Cu_{0.1}O_{3-{\alpha}}$, of which conversion was 92% at $200^{\circ}C$. By the substitution of Cu, the evolution of ${\alpha}$-oxygen was remarkably enhanced regardless of pH value at preparation step according to $O_2$-TPD. Among the different ${\alpha}$-oxygen species, the oxygen species evolved between $400^{\circ}C$ and $500^{\circ}C$, gave the better catalytic performance for selective CO oxidation including $La_{0.5}Ce_{0.5}CoO_3$ in which Cu was absent.

• Journal of Korean Society of Environmental Engineers
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• v.27 no.6
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• pp.651-656
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• 2005

Toluene, which is emitted from textile process, is considered as an important hazardous air pollutant. In this study, the catalytic activity of transition metal oxides(Cu, Mn, V, Cr, Co, Ni, Ce, Sn, Fe, Sr, Cs, Mo, La, W, Zn)/${\gamma}-Al_2O_3$ catalysts was investigated to carry out the complete oxidation of toluene. The metal catalysts were characterized by XRD-ray diffraction), FE-SEM(Field Emission Scanning Electron Micrograph), BET(Brunauer Emmett Teller) method and TPR(Temperature Programmed Reduction). Among the catalysts, Cu/${\gamma}-Al_2O_3$ was highly promising catalyst for the oxidation of toluene. From the BET results, it seems that the catalytic activity is not correlated to the specific surface area. XRD results indicated that most of catalysts exist as amorphous phase. From the FE-SEM results, it was observed that copper on ${\gamma}-Al_2O_3$ surface was well dispersed among catalysts. The catalytic activity for the toluene oxidation could be explained with that metal oxide catalyst was dispersed well over supports and was attributed to reduction activity in surface of catalysts.