Effect of doping rare earth oxide on performance of copper-manganese catalysts for water-gas shift reaction

Rare earth-doped copper-manganese mixed oxide catalysts were prepared by coprecipitation and mechanical mixing using copper sulfate, manganese sulfate, and rare-earth oxides REO （REO indicates La2O3, CeO2, Y2O3, or Pr6O11） as raw materials. The samples were characterized by X-ray diffraction （XRD）, temperature-programmed reduction （TPR）, temperature-programmed reduc-tion of oxidized surfaces （s-TPR）, and temperature-programmed desorption （TPD）. Catalytic activities were tested for a water-gas shift reaction. Doping rare earth oxides did not alter the crystal structure of the original copper-manganese mixed oxides but changed the interplanar spacing, adsorption performance and reaction performance. Doping with La2O3 enhanced the activity and stability of Cu-Mn mixed oxides because of high copper distribution and fine reduction. Doping with CeO2 and Y2O3 also decreased the reduc-tion temperatures of the samples to different degrees while improving the dispersion of Cu on the surface, thus, catalytic activity was better than that of undoped Cu-Mn sample. The Pr6O11-doped sample was difficult to reduce, the dispersion of surface coppers was lowered, resulting in poor activity.     

Effect of yttrium addition on water-gas shift reaction over CuO/CeO2 catalysts

This paper presented a study on the role of yttrium addition to CuO/CeO2 catalyst for water-gas shift reaction. A single-step co-precipitation method was used for preparation of a series of yttrium doped CuO/CeO2 catalysts with yttrium content in the range of 0-5wt.%. Properties of the obtained samples were characterized and analyzed by X-ray diffraction (XRD), Raman spectroscopy, H2-TPR, cyclic voltammetry (CV) and the BET method. The results revealed that catalytic activity was increased with the yttrium content at first, but then decreased with the further increase of yttrium content. Herein, CuO/CeO2 catalyst doped with 2wt.% of yttrium showed the highest catalytic activity (CO conversion reaches 93.4% at 250℃) and thermal stability for WGS reaction. The catalytic activity was correlated with the surface area, the area of peak y of H2-TPR profile (I.e., the reduction of surface copper oxide (crystalline forms) interacted with surface oxygen vacancies on ceria), and the area of peak C2 and A1 (Cu0→Cu2+ in cyclic voltammetry process), respectively. Besides, Raman spectra provided evidences for a synergistic Cu-Ovacancy interaction, and it was indicated that doping yttrium may facilitate the formation of oxygen vacancies on ceria.     

CuO／CeO2 Catalysts for Selective Oxidation of Carbon Monoxide in Excess Hydrogen

CuO/CeO2 catalysts were prepared by a coprecipitation method and tested for CO removal from reformed fuels via selective oxidation. The influence of the calcination temperature on the chemical compositions and catalytic performance of CuO/CeO2 catalysts were studied. It was found that CuO/CeO2 catalysts exhibit excellent CO oxidation activity and selectivity, and the complete removal of CO is attained when the catalysts are calcined at appropriate temperatures. XRD, TPR and XPS results indicate that CuO/CeO2 catalysts exhibit higher catalytic performance in CO selective oxidation due to the strong interaction between copper oxide and cerium dioxide, which promotes the dispersion and hydrogen reduction activity of copper.     

Synthesis of mesoporous CeO2-MnOx binary oxides and their catalytic performances for CO oxidation

Mesoporous CeO2-MnOx binary oxides with different Mn/Ce molar ratios were prepared by hydrothermal synthesis and characterized by scanning electron microscopy （SEM）, N2 sorption, X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS） and H2 temperature-programmed reduction （H2-TPR）. The characterization results indicated that the CeO2-MnOx catalysts exhibited flower-like microspheres with high specific surface areas, and partial Mn cations could be incorporated into CeO2 lattice to form solid solution. The CeO2-MnOx catalysts showed better catalytic activity for CO oxidation than that prepared by the coprecipitation method. Furthermore, the CeO2-MnOx catalyst with Mn/Ce molar ratio of 1 in the synthesis gel （Ce-Mn-1） exhibited the best catalytic activity, over which the conversion of CO could achieve 90% at 135 ℃. This was ascribed to presence of more Mn species with higher oxida- tion state on the surface and the better reducibility over the Ce-Mn-I catalyst than other CeO2-MnOx catalysts.     

Catalytic performance of Zr-doped CuO-CeO_2 oxides for CO selective oxidation in H_2-rich stream

Zr-doped CuO-CeO_2 catalysts for CO selective oxidation were designed and prepared by the hydrothermal method and coprecipitation. The experimental samples were characterized by means of N_2 adsorption-desorption isotherms, powder X-ray diffraction, temperature-programmed reduction and Xray photoelectron spectroscopy. It is observed that the catalyst prepared by hydrothermal method exhibits larger specific surface area, smaller crystalline size and higher dispersion of active components compared with those of the catalyst obtained by coprecipitation. Meanwhile, redox properties of copper oxide are improved significantly and highly dispersed copper species providing CO oxidation sites are present on the surface. Furthermore, adsorptive centers of CO and active oxygen species increase on the copper-ceria interfaces. The Zr-doped CuO-CeO_2 catalyst prepared by hydrothermal method possesses superior catalytic activity and selectivity for selective oxidation of CO at low temperature compared with those of the sample prepared by coprecipitation. The temperature corresponding to 50% CO conversion is only 73 ℃ and the temperature span of total CO conversion is expanded from 120 to 160 ℃.     

Effects of ZrO2 Content on Structure and Performance of Cu/CeO2-ZrO2 Catalysts for Water-Gas Shift Reaction

Water-gas shift(WGS)is a critical step in fuelprocessors for preli minary COclean-up and additionalhydrogen generation prior to the CO clean-up stage,which opened up new potential applications for WGScatalysts.Recently several formulations of noble-met-al…     

Structure and Catalytic Behavior of CuO-ZrO-CeO2 Mixed Oxides

The effect of doping CuO on the structure and properties of zirconia-ceria mixed oxide was studied. The results show that addition of CuO decreases the reduction temperature of ceria, and stabilizes the cubic structure of mixed oxides, and enhances catalytic activity of CuO-ZrO-CeO2 mixed oxides for CO oxidation. Increasing ceria content in the mixed oxides can enhance the catalytic activity, but some impurities such as sulfate make catalytic activity falling. There is little effect of calcination temperature on catalytic activities, implying that these catalysts are effective with good thermal stability.     

Catalytic Oxidative Properties and Characterization of CuO／CeO2 Catalysts

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Preparation and characterization of Ce1-xFexO2 complex oxides and its catalytic activity for methane selective oxidation

A series of Ce1-xFexO2 （x=0, 0.2, 0.4, 0.6, 0.8, 1） complex oxide catalysts were prepared using the coprecipitation method. The catalysts were characterized by means of XRD and H2-TPR. The reactions between methane and lattice oxygen from the complex oxides were investigated. The characteristic results revealed that the combination of Ce and Fe oxide in the catalysts could lower the temperature necessary to reduce the cerium oxide. The catalytic activity for selective CH4 oxidation was strongly influenced by dropped Fe species. Adding the appropriate amount of Fe2O3 to CeO2 could promote the action between CH4 and CeO2. Dispersed Fe2O3 first returned to the original state and would then virtually form the Fe species on the catalyst, which could be considered as the active site for selective CH4 oxidation. The appearance of carbon formation was significant and the oxidation of carbon appeared to be the rate-determining step; the amounts of surface reducible oxygen species in CeO2 were also relevant to the activity. Among all the catalysts, Ce0.6Fe0.402 exhibited the best activity, which converted 94.52% of CH4 at 900 ℃.     

Temperature Programmed Reduction Studies on CeO2-Containing Catalysts

Temperature programmed reduction (TPR) study was carried out for CeO2/A12O3 and CeO2/ZrO2 catalysts to evaluate oxygen storage property induced by a facile redox cycling of Ce ion. The CeO2/ZrO2 catalyst possesses excellent oxygen storage activity at 373 K after reduction above 1173 K although the oxygen storage of CeO2/Al2O3 catalyst after reduction above 1173 K is poor because of the formation of CeAlO3. Consequently, the oxygen storage on the CeO2/ZrO2 catalyst smoothly occurs from low temperatures when the catalyst is reduced even at high temperatures.     

Catalytic Reduction of SO2 on CeO2-La2O3 Rare Earth Mixed Compounds

Adding rare earth oxide CeO2 with variable valences to La2O3 formed a mixture of rare earth oxides. By means of dipping CeO2, La2O3 and their mixture, whose carriers were all γ-Al2O3, were used as the catalyst for the reduction of SO2 by CO. The activation process of this catalyst and the impact of temperature and reactant concentration on the activation process were investigated. Using X-ray diffraction, the structure characteristics of catalyst before and after reaction were analyzed to reveal the change of phase structure. The result shows that the rare earth oxide mixtures composing of CeO2 and La2O3, as the catalyst for the reduction of SO2 by CO, diminish activation temperature 50～100℃ less and have higher activity than a single oxide CeO2 or La2O3. The reason possibl is that La2O3 goes into in the lattice of CeO2 to form solid phase complex CeO2-La2O3 and increases the capability of CeO2-La2O3/γ-Al2O3 catalyst to store oxygen, which supplies the redox of CeO2 reaction with a better condition. At the same time, elemental sulfur formed in the redox reaction impels La203 to be transformed to activation phase La2O2S in a lower temperature, which can be explained with the synergism between redox reaction and COS intermediate mechanism reaction.     

Effect of BaO on Catalytic Activity of Pt-Rh TWC

The effects of BaO doping on the three-way catalytic activity of Pt-Rh catalyst and on water-gas shift were investigated. The results show that the light-off temperatures of hydrocarbon and carbon monoxide and nitrogen oxides of the fresh catalysts slightly differ from those of the aged catalysts, and the catalysts containing CeO2-ZrO2-BaO have lower lightoff temperature and better catalytic activity than these containing BaO and CeO2-ZrO2 after hydrothermal aging for 5 h at 1000 ℃. The catalysts were characterized by means of the temperature-programmed reduction （TPR） in hydrogen and the temperature-programmed desorption （TPD） in oxygen. It is confirmed that the suggested route of CeO2-ZrO2-BaO by coprecipitation can improve the catalytic activity of catalysts.     

Effect of loading content of copper oxides on performance of Mn-Cu mixed oxide catalysts for catalytic combustion of benzene

A series of Mn-Cu mixed oxide catalysts were prepared by precipitation method. The catalysts were characterized by N 2 adsorption-desorption, H 2 -TPR and XPS. When the loading ratio of manganese oxides to copper oxides was 8:2 or 7:3, the catalysts possessed better catalytic activity, and benzene was converted completely at 558 K. Results of H 2 -TPR showed that the loading of a small amount of copper oxides decreased the reduction temperature of catalysts. Results of XPS showed that the loading of a small amount of copper oxides increased the proportion of manganese and defective oxygen on the surface of catalysts, and stabilized manganese at higher oxidation state. And the catalyst with the loading ratio 7:3 was a little worse than 8:2, since the interaction between manganese oxides and copper oxides is too strong, copper oxides migrate to the surface of catalysts and manganese oxides in excess are immerged.     

Preparation of Au/CeO2 catalyst and its catalytic performance for HCHO oxidation

Aqueous precipitation and deposition-precipitation method were used to prepare CeO2 supports and Au/CeO2 catalysts, respectively. The effect of preparation condition of support on the catalyst activity was investigated. The catalytic combustion of HCHO was considered as the probe reaction for comparing the catalyst activity. The BET, X-ray diffraction, X-ray photoelectron spectroscopy （XPS）, and reduction （TPR） were carried out to analyze the influence factor on the catalysts activity. The results showed that the addition of dispersant and use of microwave in the support preparation procedure could be beneficial for enhancing the interaction of supports and gold species and thus improved the catalytic activity. The total conversion temperature for HCHO was 146 ℃ over AC400. With the modification during supports preparation process, the catalytic activity increased with total conversion temperature decreasing to 98 ℃. The results of XPS indicated that Au^0 and Au^＋1 species coexisted in these catalysts and the activity of catalyst correlated with Au^＋1/Au^0 ratio. Temperature-programmed reduction results demonstrated that the reduction peak appeared between 100-170 ℃ with the inducing of gold. The dependence of activity on the reduction peak temperature implied that ionic gold was catalytic activity component for HCHO oxidation.     

Effect of water vapor on the CO and CH4 catalytic oxidation over CeO2-Mox (M=Cu,Mn,Fe,Co,and Ni) mixed oxide

CeO2-MOx (M=Cu, Mn, Fe, Co, and Ni) mixed oxide catalysts were prepared by a citric acid complexation-combustion method. CeO2-MOx solid solutions could be formed with M cations doping into CeO2 lattice, while NiO and Co3O4 phases were detected on the surface of CeO2-NiO and CeO2-Co3O4 by Raman spectroscopy. The presence of M in CeO2 could obviously promote its catalytic activity for CH4 catalytic combustion and CO oxidation. Among the prepared samples, CeO2-CuO exhibited the best performance for CO oxidatio...     

Synthesis of Ti-Ce-Si Binary and Ternary Nanocomposite Photocatalyst by Supercritical Fluid Drying Technology

Recently,photodegratation of various organiccontaminants with powdered semiconductors as cata-lysts has received much attention for their potential inthe utilization of light energy.TiO2is one of the mostwidely used photocatalysts due toits relatively nontox-ic,high activity,strong oxidizing property,and excel-lent stability.However,some weaknesses such as poormechanic strength,compressive strength and thermalstability have li mited its industrial applications.Therefore,it is necessary to i mp…     

Preparation,characterization and catalytic oxidation property of CeO2/Cu2+-attapulgite （ATP） nanocomposites

Cerium oxide(CeO2) coated on copper modified attapulgite clay nanocomoposite(CeO2/Cu2+-ATP) was prepared by homogeneous deposition method.The microstructures of the as-prepared CeO2/Cu2+-ATP nanocomposites were characterized by X-ray diffraction(XRD),energy-dispersive spectrometer(EDS) and transmission electron microscopy(TEM).The results indicated that CeO2 particles with average size of about 5 nm were loaded onto the Cu2+-ATP and were widely dispersed.Comparing the catalytic activity of ATP/CeO2 and CeO2/Cu2+-ATP,the catalytic activity was improved when a small quantity of Cu2+ was introduced.The loading amount of CeO2 and reaction temperature had important effects on decolorization ratio of methyl orange(MO).When the loading amount and reaction temperature were 70% and 338 K,respectively,the decolorization ratio of MO reached over 99%,which showed excellent catalytic activity.     

Study on Catalysts with Rhodium Loading on Different Cerium-Zirconium Mixed Oxides

The catalysts with Rh loading on different cerium-zirconium mixed oxides were characterized by BET, H2-TPR and OSC. The effects of different cerium-zirconium mixed oxides on catalytic performance and thermal stability of Rh loaded catalyst were studied. The results show that: (1) Rh can enhance cerium-zirconium mixed oxides OSC and catalytic reaction rates; (2) cerium-zirconium mixed oxides with high Ce contents and low Zr contents are more favorable to the stability of catalysts. Moreover, the contents of CeO2 have important effect on catalysts characteristics, and the addition of some rare earth components, such as La, Pr and Nd also have some influences.     

A comparative study of formaldehyde and carbon monoxide complete oxidation on MnOx-CeO2 catalysts

MnOx-CeO2 composite catalysts were prepared by a coprecipitation method and tested for formaldehyde (HCHO) and carbon monoxide (CO) oxidation. X-ray photon spectroscopy (XPS) results indicated that the average oxidation state of surface Mn species in CeMn composite catalyst was higher compared to the pure MnOx. The enhancement of reactivity for HCHO oxidation was due to the activation of the lattice oxygen species in MnOx by the addition of CeO2, which was confirmed by the H2 temperature programmed reduction (H2-TPR) results. The remarkable enhancement of reactivity for CO oxidation by the addition of CeO2 was due to the active oxygen species generated on the CeO2 surface which directly participated in the reaction.     

Preparation of High-Surface Area Nano-CeO2 by Template-Assisted Precipitation Method

The high-surface area nano-CeO2 was prepared by Ce（NO3）3 by precipitation method, with surfactant cetyhrimethyl ammonium bromide （CTAB） as templating agent. The effects of the precipitating agents, reaction temperature, ageing time, and calcination temperature on the surface area, as well as the pore structure and the mean crystallite size of nano-CeO2 were studied. It was found that the reaction of Ce（NO3）3 with NaOH in the presence of CTAB at 90℃ for 12 h yieldsed a cerium oxide/surfaetant mixture, which after calcination at 400℃ resulted in high-surface area nano-CeO2. The mean crystallite size of CeO2 was approximately 6 nm, surface area was in excess of 200 m^2· g ^- 1, pore size was approximately 9 nm, and the pore distribution was concentrative. Moreover, the surface area can still reach 147 m^2·g^- 1 after calcination at 700 ℃, which showed the good thermal stability of the CeO2. The number of oxygen vacancies in the structure of CeO2 corresponded with the surface area of CeO2, and the high surface area was propitious to the formalion of oxygen vacancies.