Ce0.6Zr0.4O2 solid solution ultrafine particle was prepared in the cyclohexane/water/OP-10/n-hexanol reversed microemulsion. The quasi-ternary phase diagram investigations showed that the system has narrow W/O type mi...Ce0.6Zr0.4O2 solid solution ultrafine particle was prepared in the cyclohexane/water/OP-10/n-hexanol reversed microemulsion. The quasi-ternary phase diagram investigations showed that the system has narrow W/O type microemulison region, so it is the proper system to prepare Ce0.6Zr0.4O2 solid solution ultrafine particle. Some physical-chemical techniques such as TG/DTA, XRD, BET, and HRTEM are used to characterize the resultant powders. The results show that the fluorite cubic Ce0.6Zr0.4O2 solid solution is obtained at 400 ℃. The surface area is （146.7 m^2·g^-1）, which is higher than the surface area for sol-gel prepared sample （59.5m^2·g^-1）. HRTEM images indicated that the Ce0.6Zr0.4O2 solid solution ultrafine particle is well-crystallized, narrow size distribution, less agglomeration, within mean size of 5 -7 nm.展开更多
The structure and catalytic desulfurization characteristics of CeO2-TiO2 mixed oxides were investigated by means ofX-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS） and catalytic activity tests. Acco...The structure and catalytic desulfurization characteristics of CeO2-TiO2 mixed oxides were investigated by means ofX-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS） and catalytic activity tests. According to the results, a CeO2-TiO2solid solution is formed when the mole ratio of cerium to titanium n（Ce）：n（Ti） is 5：5 or greater, and the most suitable n（Ce）：n（Ti） isdetermined as 7：3, over which the conversion rate of SO2 and the yield of sulfur at 500℃ reach 93% and 99%, respectively.According to the activity testing curve, Ce0.7Ti0.3O2 （n（Ce）：n（Ti）=7：3） without any pretreatment can be gradually activated by reagentgas after about 10 min, and reaches a steady activation status 60 min later. The XPS results of Ce0.7Ti0.3O2 after different time ofSO2＋CO reaction show that CeO2 is the active component that offers the redox couple Ce4＋/Ce3＋ and the labile oxygen vacancies, andTiO2 only functions as a catalyst structure stabilizer during the catalytic reaction process. After 48 h of catalytic reaction at 500℃,Ce0.7Ti0.3O2 still maintains a stable structure without being vulcanized, demonstrating its good anti-sulfur poisoning performance.展开更多
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 ...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...展开更多
CeO2-ZeO2 solid solutions are extensively used as oxygen storage promoters in the current automotive three-way catalysts. High thermal stability of the textural properties is one of the most important requirements for...CeO2-ZeO2 solid solutions are extensively used as oxygen storage promoters in the current automotive three-way catalysts. High thermal stability of the textural properties is one of the most important requirements for practical application since temperatures up to 1273 K are easily experienced by these materials under real working conditions. In the present paper, we investigated how hydrothermal treatments applied to cakes of doped and undoped ZrO2-rich CeO2-ZrO2 precursors might improve the thermal stability of the final CeO2-ZrO2 solid solution. A rationale was developed that allowed to correlate the morphology of the hydrothermaUy treated cake with the thermal stability at 1273 K of the final product, which did not depend on the composition of the mixed oxides.展开更多
CeO2-ZrO2-Al2O3 ternary oxides were successfully prepared by a green route of supercritical anti-solvent precipitation with supercritical CO2 as anti-solvent and methanol as solvent. The structures and oxygen storage ...CeO2-ZrO2-Al2O3 ternary oxides were successfully prepared by a green route of supercritical anti-solvent precipitation with supercritical CO2 as anti-solvent and methanol as solvent. The structures and oxygen storage capacities of these ternary oxides were characterized by XRD, Raman spectra and oxygen storage capacity measurements. It was found that Al3＋ and Zr4＋ inserted into CeO2 lattice, forming CeO2-ZrO2-Al2O3 solid solution. The concentration of aluminium isopropoxide in the solution affected the concentration of oxygen vacancy and the distortion of oxygen sublattice which were responsible for the oxygen storage capacity. The rapidest oxygen uptake/release rate and maximum total oxygen storage capacity （122.0 mmolO2/molCeO2） were obtained with the aluminitun isopropoxide concentration at 0.2 wt.% in the solution.展开更多
A series of CeO2–ZrO2–WO3（CZW）catalysts prepared by a hydrothermal synthesis method showed excellent catalytic activity for selective catalytic reduction（SCR）of NO with NH3 over a wide temperature of 150–550℃....A series of CeO2–ZrO2–WO3（CZW）catalysts prepared by a hydrothermal synthesis method showed excellent catalytic activity for selective catalytic reduction（SCR）of NO with NH3 over a wide temperature of 150–550℃.The effect of hydrothermal treatment of CZW catalysts on SCR activity was investigated in the presence of 10% H2O.The fresh catalyst showed above 90% NOx conversion at 201–459℃,which is applicable to diesel exhaust NOx purification（200–440℃）.The SCR activity results indicated that hydrothermal aging decreased the SCR activity of CZW at low temperatures（below 300℃）,while the activity was notably enhanced at high temperature（above 450℃）.The aged CZW catalyst（hydrothermal aging at 700℃ for 8 hr）showed almost 80% NOx conversion at 229–550℃,while the V2O5–WO3/TiO2 catalyst presented above 80% NOx conversion at 308–370℃.The effect of structural changes,acidity,and redox properties of CZW on the SCR activity was investigated.The results indicated that the excellent hydrothermal stability of CZW was mainly due to the CeO2–ZrO2 solid solution,amorphous WO3 phase and optimal acidity.In addition,the formation of WO3 clusters increased in size as the hydrothermal aging temperature increased,resulting in the collapse of structure,which could further affect the acidity and redox properties.展开更多
Using nanoparticles of CeO2 and ZrO2 prepared by the chemical precipitation method as starting materials, the single-phase cubic Ce0.5Zr0.5O2 solid solution (c-Ce0.5Z0.5O2) has been synthesized under 3.1 GPa at 1073 K...Using nanoparticles of CeO2 and ZrO2 prepared by the chemical precipitation method as starting materials, the single-phase cubic Ce0.5Zr0.5O2 solid solution (c-Ce0.5Z0.5O2) has been synthesized under 3.1 GPa at 1073 K for the first time. The structure of the c-Ce0.5Zr0.5O2 has not been changed before and after annealing at 773 K for 1 h. Only an unknown EPR signal (g =1.990) has been observed in the c-Ce0.5Zr0.5O2 and not varied after annealing at 773 K for 1 h, which exhibited that there exists no Ce3+ in the c-Ce0.5Zr0.5O2 and the Ce4+ has not been reduced into Ce3+ after annealing. The transport mechanism is ionic for the c-Ce0.5Zr0.5O2. The bulk conductivity (a =1.2×10-5 S/cm at 823 K, σ=2.1 ×10-3 S/cm at 1123 K) is the same as that of CeO2, but smaller than that of Y2O3-stabilized ZrO2. A marked curvature at T = 823 K has been observed in the Arrhenius plot of the bulk conductivity. The activation energy below 823 K is lower than that above 823 K, and the reason has been discussed.展开更多
Codoping approach is an appealing strategy to further improve the catalytic activity of Ce-based catalysts.In the present study,Mn and/or Cu doped ceria solid solutions MnxCuyCe1-x-yO2,CuxCe1-xO2,MnxCe1-xO2 and pure C...Codoping approach is an appealing strategy to further improve the catalytic activity of Ce-based catalysts.In the present study,Mn and/or Cu doped ceria solid solutions MnxCuyCe1-x-yO2,CuxCe1-xO2,MnxCe1-xO2 and pure CeO2 were prepared by CTAB-assisted hydrothermal method for CO oxidation.XRD,SEM,EDS,BET,Raman,H2-TPR,XPS and in situ DRIFTS techniques were carried out to study the physicochemical properties and to correlate them to the activity.The doped samples maintain the cubic fluorite structure of CeO2 with high crystallinity and small crystallite size,forming Ce-based solid solutions.The obtained catalysts have large mesoporous structure with average pore size of 10-14 nm.The doped transition metal enhances the oxygen vacancies and improves reducibility of the solids.The synergistic interaction of Mn and Cu codoping induces mo re oxygen vacancies,pro moting the increase of surface adsorbed oxygen and the transfer of bulk oxygen of catalyst,thereby enhancing the catalytic activity for CO oxidation.Besides,the decomposition rate of the carbonate species which is derived from in situ DRIFTS for each catalyst can provide a measure to evaluate its catalytic activity of CO oxidation.展开更多
Single-phase homogeneous Ce1-x ZrxO2 solid versed microemulsion method. The structural properties solutions with various compositions were synthesized using the reand performance of Ce1- xZrxO2 were studied using XRD,...Single-phase homogeneous Ce1-x ZrxO2 solid versed microemulsion method. The structural properties solutions with various compositions were synthesized using the reand performance of Ce1- xZrxO2 were studied using XRD, BET, SEM, HRTEM, TPR and CO oxidation measurements. The results show that in the range of x = 0.4 - 0.5 and x = 0.6 - 1.0, the solid solutions posses the cubic and the tetragonal phase structure, respectively, Solids obtained by the reversed microemulsion method were more homogeneous on the whole range of composition, XRD investigations of the prepared materials did not show segregation of cerium or zirconium oxides, Highly uniform nanosize solid solution particles of ceria-zirconia with high specific area （146.7 m^2·g^-1） were attained under the conditions of this study. The TPR results and CO oxidation measurements indicate that the performance of the CeO2-ZrO2 mixed oxides is strongly related to the composition and structure of the oxides. Enhancement of the activity was found for the catalyst prepared by reversed microemulsion method as compared to the sample prepared by sol-gel method.展开更多
文摘Ce0.6Zr0.4O2 solid solution ultrafine particle was prepared in the cyclohexane/water/OP-10/n-hexanol reversed microemulsion. The quasi-ternary phase diagram investigations showed that the system has narrow W/O type microemulison region, so it is the proper system to prepare Ce0.6Zr0.4O2 solid solution ultrafine particle. Some physical-chemical techniques such as TG/DTA, XRD, BET, and HRTEM are used to characterize the resultant powders. The results show that the fluorite cubic Ce0.6Zr0.4O2 solid solution is obtained at 400 ℃. The surface area is （146.7 m^2·g^-1）, which is higher than the surface area for sol-gel prepared sample （59.5m^2·g^-1）. HRTEM images indicated that the Ce0.6Zr0.4O2 solid solution ultrafine particle is well-crystallized, narrow size distribution, less agglomeration, within mean size of 5 -7 nm.
文摘The structure and catalytic desulfurization characteristics of CeO2-TiO2 mixed oxides were investigated by means ofX-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS） and catalytic activity tests. According to the results, a CeO2-TiO2solid solution is formed when the mole ratio of cerium to titanium n（Ce）：n（Ti） is 5：5 or greater, and the most suitable n（Ce）：n（Ti） isdetermined as 7：3, over which the conversion rate of SO2 and the yield of sulfur at 500℃ reach 93% and 99%, respectively.According to the activity testing curve, Ce0.7Ti0.3O2 （n（Ce）：n（Ti）=7：3） without any pretreatment can be gradually activated by reagentgas after about 10 min, and reaches a steady activation status 60 min later. The XPS results of Ce0.7Ti0.3O2 after different time ofSO2＋CO reaction show that CeO2 is the active component that offers the redox couple Ce4＋/Ce3＋ and the labile oxygen vacancies, andTiO2 only functions as a catalyst structure stabilizer during the catalytic reaction process. After 48 h of catalytic reaction at 500℃,Ce0.7Ti0.3O2 still maintains a stable structure without being vulcanized, demonstrating its good anti-sulfur poisoning performance.
基金Project supported by the National Basic Research Program of China (2010CB732300)the National Key Technologies R&D Program of China (2007BAJ03B01)the National Natural Science Foundation of China (20601008)
文摘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...
基金PRIN 2006, "Caratterizzazione spettroscopica e morfologica di Me-POSS eterogeneizzati", MEL Chemicals
文摘CeO2-ZeO2 solid solutions are extensively used as oxygen storage promoters in the current automotive three-way catalysts. High thermal stability of the textural properties is one of the most important requirements for practical application since temperatures up to 1273 K are easily experienced by these materials under real working conditions. In the present paper, we investigated how hydrothermal treatments applied to cakes of doped and undoped ZrO2-rich CeO2-ZrO2 precursors might improve the thermal stability of the final CeO2-ZrO2 solid solution. A rationale was developed that allowed to correlate the morphology of the hydrothermaUy treated cake with the thermal stability at 1273 K of the final product, which did not depend on the composition of the mixed oxides.
基金National Natural Science Foundation of China(20976120)the Natural Science Foundation of Tianjin(09JCYBJC06200)
文摘CeO2-ZrO2-Al2O3 ternary oxides were successfully prepared by a green route of supercritical anti-solvent precipitation with supercritical CO2 as anti-solvent and methanol as solvent. The structures and oxygen storage capacities of these ternary oxides were characterized by XRD, Raman spectra and oxygen storage capacity measurements. It was found that Al3＋ and Zr4＋ inserted into CeO2 lattice, forming CeO2-ZrO2-Al2O3 solid solution. The concentration of aluminium isopropoxide in the solution affected the concentration of oxygen vacancy and the distortion of oxygen sublattice which were responsible for the oxygen storage capacity. The rapidest oxygen uptake/release rate and maximum total oxygen storage capacity （122.0 mmolO2/molCeO2） were obtained with the aluminitun isopropoxide concentration at 0.2 wt.% in the solution.
基金supported by the National Natural Science Foundation of China(Nos.U1137603,21307047)the Opening Project of Key Laboratory of Green Catalysis of Sichuan Institutes of High Education(No.LYJ1309)
文摘A series of CeO2–ZrO2–WO3（CZW）catalysts prepared by a hydrothermal synthesis method showed excellent catalytic activity for selective catalytic reduction（SCR）of NO with NH3 over a wide temperature of 150–550℃.The effect of hydrothermal treatment of CZW catalysts on SCR activity was investigated in the presence of 10% H2O.The fresh catalyst showed above 90% NOx conversion at 201–459℃,which is applicable to diesel exhaust NOx purification（200–440℃）.The SCR activity results indicated that hydrothermal aging decreased the SCR activity of CZW at low temperatures（below 300℃）,while the activity was notably enhanced at high temperature（above 450℃）.The aged CZW catalyst（hydrothermal aging at 700℃ for 8 hr）showed almost 80% NOx conversion at 229–550℃,while the V2O5–WO3/TiO2 catalyst presented above 80% NOx conversion at 308–370℃.The effect of structural changes,acidity,and redox properties of CZW on the SCR activity was investigated.The results indicated that the excellent hydrothermal stability of CZW was mainly due to the CeO2–ZrO2 solid solution,amorphous WO3 phase and optimal acidity.In addition,the formation of WO3 clusters increased in size as the hydrothermal aging temperature increased,resulting in the collapse of structure,which could further affect the acidity and redox properties.
基金This work was supported by the National Natural Science Foundation of China (Grant No. 19874023).
文摘Using nanoparticles of CeO2 and ZrO2 prepared by the chemical precipitation method as starting materials, the single-phase cubic Ce0.5Zr0.5O2 solid solution (c-Ce0.5Z0.5O2) has been synthesized under 3.1 GPa at 1073 K for the first time. The structure of the c-Ce0.5Zr0.5O2 has not been changed before and after annealing at 773 K for 1 h. Only an unknown EPR signal (g =1.990) has been observed in the c-Ce0.5Zr0.5O2 and not varied after annealing at 773 K for 1 h, which exhibited that there exists no Ce3+ in the c-Ce0.5Zr0.5O2 and the Ce4+ has not been reduced into Ce3+ after annealing. The transport mechanism is ionic for the c-Ce0.5Zr0.5O2. The bulk conductivity (a =1.2×10-5 S/cm at 823 K, σ=2.1 ×10-3 S/cm at 1123 K) is the same as that of CeO2, but smaller than that of Y2O3-stabilized ZrO2. A marked curvature at T = 823 K has been observed in the Arrhenius plot of the bulk conductivity. The activation energy below 823 K is lower than that above 823 K, and the reason has been discussed.
基金Project supported by the National Natural Science Foundation of China(21777055)Shandong Provincial Natural Science Foundation(ZR2017BB004)+1 种基金Shandong Province Key Research and Development Plan(2017GGX202004)Shandong Province Major Science and Technology Innovation Project(2017CXGC1004)
文摘Codoping approach is an appealing strategy to further improve the catalytic activity of Ce-based catalysts.In the present study,Mn and/or Cu doped ceria solid solutions MnxCuyCe1-x-yO2,CuxCe1-xO2,MnxCe1-xO2 and pure CeO2 were prepared by CTAB-assisted hydrothermal method for CO oxidation.XRD,SEM,EDS,BET,Raman,H2-TPR,XPS and in situ DRIFTS techniques were carried out to study the physicochemical properties and to correlate them to the activity.The doped samples maintain the cubic fluorite structure of CeO2 with high crystallinity and small crystallite size,forming Ce-based solid solutions.The obtained catalysts have large mesoporous structure with average pore size of 10-14 nm.The doped transition metal enhances the oxygen vacancies and improves reducibility of the solids.The synergistic interaction of Mn and Cu codoping induces mo re oxygen vacancies,pro moting the increase of surface adsorbed oxygen and the transfer of bulk oxygen of catalyst,thereby enhancing the catalytic activity for CO oxidation.Besides,the decomposition rate of the carbonate species which is derived from in situ DRIFTS for each catalyst can provide a measure to evaluate its catalytic activity of CO oxidation.
文摘Single-phase homogeneous Ce1-x ZrxO2 solid versed microemulsion method. The structural properties solutions with various compositions were synthesized using the reand performance of Ce1- xZrxO2 were studied using XRD, BET, SEM, HRTEM, TPR and CO oxidation measurements. The results show that in the range of x = 0.4 - 0.5 and x = 0.6 - 1.0, the solid solutions posses the cubic and the tetragonal phase structure, respectively, Solids obtained by the reversed microemulsion method were more homogeneous on the whole range of composition, XRD investigations of the prepared materials did not show segregation of cerium or zirconium oxides, Highly uniform nanosize solid solution particles of ceria-zirconia with high specific area （146.7 m^2·g^-1） were attained under the conditions of this study. The TPR results and CO oxidation measurements indicate that the performance of the CeO2-ZrO2 mixed oxides is strongly related to the composition and structure of the oxides. Enhancement of the activity was found for the catalyst prepared by reversed microemulsion method as compared to the sample prepared by sol-gel method.
