The influences of CeO2-ZrO2 and γ-Al2O3 mixing methods on the catalytic activity and stability of partial oxidation of methane (POM) were investigated over Ni/Ce0.7Zr0.3O2-Al2O3 catalysts. The catalysts were charac...The influences of CeO2-ZrO2 and γ-Al2O3 mixing methods on the catalytic activity and stability of partial oxidation of methane (POM) were investigated over Ni/Ce0.7Zr0.3O2-Al2O3 catalysts. The catalysts were characterized by XRD, TPR, H2-chemsorption, and TG-DTA. For fresh catalysts, the results showed that the salt precursor mixing catalyst (ATOM) presented better performance than the catalysts prepared by the precipitator mixing method (MOL) and the powder mechanically mixing method (MECH). The result of XRD suggested that the interaction between CeO2-ZrO2 and Al2O3 in ATOM sample was stronger than the others, which led to more lattice defects and thereby better initial activity. Moreover, the MECH sample had the best stability and the least coke deposition in 24 h stability tests. The results of TPR and H2-chemsorption indicated that the intimate contact of Ni-Al in MECH sample enhanced the ability of resisting coke deposition and metal sintering.展开更多
The catalytic behaviors of Pd(1.4 wt%)catalysts supported on CeO2-ZrO2-La2O3 mixed oxides with different Ce/Zr molar ratios were investigated for methanol decomposition.Nitrogen adsorption-desorption(BET),X-ray photoe...The catalytic behaviors of Pd(1.4 wt%)catalysts supported on CeO2-ZrO2-La2O3 mixed oxides with different Ce/Zr molar ratios were investigated for methanol decomposition.Nitrogen adsorption-desorption(BET),X-ray photoelectron spectroscopy(XPS),H2 temperature-programmed reduction(H2-TPR),X-ray diffraction(XRD)and Pd dispersion analysis were used for their characterization.Pd/Cc0.76Zro.18 La0.06O1.97 catalyst showed the highest BET surface area,best Pd dispersion capability and strongest metal-support interaction.Moreover,XPS showed that there was lattice defect oxygen or mobile oxygen.According to the result of O 1s measurements the lattice defect oxygen or mobile oxygen helped to maintain Pd in a partly oxidized state and increased the activity for methanol decomposition.The Pd/Ce0.76Zr0.18La0.0601.97 catalyst exhibited the best activity.A 100%conversion of methanol was achieved at around 260°C,which was about 20-40°C lower than other catalysts.展开更多
A series of CeO2-ZrO2-WO3 catalysts for the selective catalytic reduction (SCR) of NO with NH3 were prepared by hydrothermal method. The influence of calcination temperature on the catalytic activity, microstructure...A series of CeO2-ZrO2-WO3 catalysts for the selective catalytic reduction (SCR) of NO with NH3 were prepared by hydrothermal method. The influence of calcination temperature on the catalytic activity, microstructure, surface acidity and redox behavior of CeO2-ZrO2-WO3 catalyst was investigated using various characterization methods. It was found that the CeO2-ZrO2-WO3 catalyst calcined at 600 ℃ showed the best catalytic performance and excellent N2 selectivity, and yielded more than 90% NO conversion in a wide temperature range of 250-500 ℃ with a space velocity (GHSV) of 60000 131. As the calcination temperature was increased from 400 to 600 ℃, the NO conversion obviously increased, but decreased at higher calcination temperature. The results implied that the higher surface area, the strongest synergistic interaction, the superior redox property and the highly dispersed or amorphous WO3 species contributed to the excellent SCR activity of the CeO2-ZrO2-WO3 catalyst calcined at 600℃.展开更多
CeO2-based oxygen materials were prepared with co-precipitation method and characterized via Brunauer-Emmet Teller(BET)method,X-ray diffraction(XRD)and temperature-programmed reduction(H2-TPR).This paper revealed that...CeO2-based oxygen materials were prepared with co-precipitation method and characterized via Brunauer-Emmet Teller(BET)method,X-ray diffraction(XRD)and temperature-programmed reduction(H2-TPR).This paper revealed that three CeO2-based oxygen storage materials are all forming homogeneous solid solution.Among the samples,CeO2-ZrO2-Al2O3(CZA)has the best textural properties and excellent thermal stability.The specific surface area and pore volume of aged CZA are 90 m2/g and 0.29 mL/g.We proposed a viewpoint:Al3+ might insert among the interspace of fluorite structure or highly dispersal in solid solutions.展开更多
Two-step steam reforming of methane (SRM) is a novel chemical looping process towards the production of pure hydrogen and syngas (synthesis gas), consisting of a syngas production step and a water-splitting step. Rene...Two-step steam reforming of methane (SRM) is a novel chemical looping process towards the production of pure hydrogen and syngas (synthesis gas), consisting of a syngas production step and a water-splitting step. Renewable energy can be used to drive this process for hydrogen production, especially solar energy. CeO2-Fe2O3 complex oxide oxygen carrier was prepared by the impregnation method and characterized by means of X-ray diffractometer (XRD), Raman spectroscopy (Raman) and hydrogen programmed reduction (H2-TPR). CH4 temperature programmed and isothermal reactions were adopted to test syngas production reactivity, and water splitting reaction was employed to investigate water-splitting activity. Moreover, two-step SRM performance was evaluated by a successive redox cycle. The results showed that CO-uncontaminated H2 and highly selective syngas (with H2/CO ratio close to 2) could be respectively obtained from two steps, and CeFeO3 formation was found in the first redox cycle and proved to be enhanced by the redox treatment. After 10 successive cycles, obvious CeFeO3 phase was detected, which may be responsible for favorable successive redox cycle performances.展开更多
Ce-Zr-Al-Nd2O3 (CZAN) support materials were prepared by co-precipitation and impregnation methods, respectively. They were characterized by X-ray diffTaction (XRD), low temperature nitrogen adsorption-desorption,...Ce-Zr-Al-Nd2O3 (CZAN) support materials were prepared by co-precipitation and impregnation methods, respectively. They were characterized by X-ray diffTaction (XRD), low temperature nitrogen adsorption-desorption, oxygen pulsing technique, H2-temperamre programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS). The Pd-only three-way catalysts (Pd-TWC) supported on these materials were prepared by incipient wetness method and studied by activity tests. The results demonstrated that the CZAN supports obtained by the two methods showed better structural, textural and redox properties than the CZA without Nd2O3, and the addition of Nd203 improved the catalytic activity of TWC. Especially, the CZAN-i support prepared by impregnation method had better thermal stability and redox property. Meanwhile, the Pd/CZAN-i catalyst exhibited the best catalytic performance. XPS measurements indicated that the Nd-modified samples possessed more Ce3+ and oxygen vacancies on the surface of samples, which led to a better redox property. The excellent redox property of support materials helped to improve the catalytic activity of TWC.展开更多
Nickel catalysts supported on CeO2-ZrO2-CeO2,ZrO2-Al2O3 and Al2O3 were prepared and characterized by means of X-ray diffraction(XRD),BET areas,H2 temperature-programmed reduction(H2-TPR),and X-ray photoelectron sp...Nickel catalysts supported on CeO2-ZrO2-CeO2,ZrO2-Al2O3 and Al2O3 were prepared and characterized by means of X-ray diffraction(XRD),BET areas,H2 temperature-programmed reduction(H2-TPR),and X-ray photoelectron spectroscopy(XPS).Through the test of catalytic partial oxidation of methane(CPOM),Ni/CeO2-ZrO2-Al2O3 displayed the highest activity,which resulted from its largest BET area and best NiO dispersion.Furthermore,Ni/CeO2-ZrO2-Al2O3 maintained a long-time stability in CPOM,which was attributed to its best coking resistance among all the prepared catalysts.展开更多
The Pd-only catalysts for motorcycle were prepared by impregnating CeO2-ZrO2-Al2O3 and CeO2-ZrO2+Al2O3 with PdCl2 aqueous solution and characterized by X-ray diffraction (XRD), oxygen storage capacity (OSC) and H2-tem...The Pd-only catalysts for motorcycle were prepared by impregnating CeO2-ZrO2-Al2O3 and CeO2-ZrO2+Al2O3 with PdCl2 aqueous solution and characterized by X-ray diffraction (XRD), oxygen storage capacity (OSC) and H2-temperature-programmed reduction (H2-TPR) methods. The XRD result indicated that the CeO2-ZrO2-Al2O3 compound prepared by co-precipitation formed a single solid solution and had good thermal stability, and Pd phase was not observed in all catalysts. The TPR results showed that the reduction temperature of Pd/CeO2-ZrO2-Al2O3 catalyst was lower than that of Pd/CeO2-ZrO2+Al2O3 catalyst whether they were fresh or aged catalysts. The Pd/CeO2-ZrO2-Al2O3 exhibited high three-way catalytic activity at low temperature, high thermal stability, and wide working window, suggesting a great potential for applications.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 uptakeelease 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
基金973 Program (2004CB719503)Key Program of Natural Science Foundation of Tianjin (07JCZDJC01600)Program for New Century Excellent Talents in University (NCET-06-0243)
摘要The influences of CeO2-ZrO2 and γ-Al2O3 mixing methods on the catalytic activity and stability of partial oxidation of methane (POM) were investigated over Ni/Ce0.7Zr0.3O2-Al2O3 catalysts. The catalysts were characterized by XRD, TPR, H2-chemsorption, and TG-DTA. For fresh catalysts, the results showed that the salt precursor mixing catalyst (ATOM) presented better performance than the catalysts prepared by the precipitator mixing method (MOL) and the powder mechanically mixing method (MECH). The result of XRD suggested that the interaction between CeO2-ZrO2 and Al2O3 in ATOM sample was stronger than the others, which led to more lattice defects and thereby better initial activity. Moreover, the MECH sample had the best stability and the least coke deposition in 24 h stability tests. The results of TPR and H2-chemsorption indicated that the intimate contact of Ni-Al in MECH sample enhanced the ability of resisting coke deposition and metal sintering.
基金the National Natural Science Foundation of China(20773090)the Specialized Research Fund for the Doctoral Program of Higher Education of China(20070610026,200806100009)
摘要The catalytic behaviors of Pd(1.4 wt%)catalysts supported on CeO2-ZrO2-La2O3 mixed oxides with different Ce/Zr molar ratios were investigated for methanol decomposition.Nitrogen adsorption-desorption(BET),X-ray photoelectron spectroscopy(XPS),H2 temperature-programmed reduction(H2-TPR),X-ray diffraction(XRD)and Pd dispersion analysis were used for their characterization.Pd/Cc0.76Zro.18 La0.06O1.97 catalyst showed the highest BET surface area,best Pd dispersion capability and strongest metal-support interaction.Moreover,XPS showed that there was lattice defect oxygen or mobile oxygen.According to the result of O 1s measurements the lattice defect oxygen or mobile oxygen helped to maintain Pd in a partly oxidized state and increased the activity for methanol decomposition.The Pd/Ce0.76Zr0.18La0.0601.97 catalyst exhibited the best activity.A 100%conversion of methanol was achieved at around 260°C,which was about 20-40°C lower than other catalysts.
基金Project supported by the National Natural Science Foundation of China(21377048,21307047)the Opening Project of Key Laboratory of Green Catalysis of Sichuan Institutes of High Education(LYJ1309)
摘要A series of CeO2-ZrO2-WO3 catalysts for the selective catalytic reduction (SCR) of NO with NH3 were prepared by hydrothermal method. The influence of calcination temperature on the catalytic activity, microstructure, surface acidity and redox behavior of CeO2-ZrO2-WO3 catalyst was investigated using various characterization methods. It was found that the CeO2-ZrO2-WO3 catalyst calcined at 600 ℃ showed the best catalytic performance and excellent N2 selectivity, and yielded more than 90% NO conversion in a wide temperature range of 250-500 ℃ with a space velocity (GHSV) of 60000 131. As the calcination temperature was increased from 400 to 600 ℃, the NO conversion obviously increased, but decreased at higher calcination temperature. The results implied that the higher surface area, the strongest synergistic interaction, the superior redox property and the highly dispersed or amorphous WO3 species contributed to the excellent SCR activity of the CeO2-ZrO2-WO3 catalyst calcined at 600℃.
摘要CeO2-based oxygen materials were prepared with co-precipitation method and characterized via Brunauer-Emmet Teller(BET)method,X-ray diffraction(XRD)and temperature-programmed reduction(H2-TPR).This paper revealed that three CeO2-based oxygen storage materials are all forming homogeneous solid solution.Among the samples,CeO2-ZrO2-Al2O3(CZA)has the best textural properties and excellent thermal stability.The specific surface area and pore volume of aged CZA are 90 m2/g and 0.29 mL/g.We proposed a viewpoint:Al3+ might insert among the interspace of fluorite structure or highly dispersal in solid solutions.
基金Project support by the National Natural Science Foundation of China (50574046, 50774038)the Natural Science Foundation of Yunnan Prov-ince (2008E030M)+1 种基金the Research Fund for the Doctoral Program of Higher Education of China (20095314120005)2010 Innovation Fund of Kunming University of Science and Technology
摘要Two-step steam reforming of methane (SRM) is a novel chemical looping process towards the production of pure hydrogen and syngas (synthesis gas), consisting of a syngas production step and a water-splitting step. Renewable energy can be used to drive this process for hydrogen production, especially solar energy. CeO2-Fe2O3 complex oxide oxygen carrier was prepared by the impregnation method and characterized by means of X-ray diffractometer (XRD), Raman spectroscopy (Raman) and hydrogen programmed reduction (H2-TPR). CH4 temperature programmed and isothermal reactions were adopted to test syngas production reactivity, and water splitting reaction was employed to investigate water-splitting activity. Moreover, two-step SRM performance was evaluated by a successive redox cycle. The results showed that CO-uncontaminated H2 and highly selective syngas (with H2/CO ratio close to 2) could be respectively obtained from two steps, and CeFeO3 formation was found in the first redox cycle and proved to be enhanced by the redox treatment. After 10 successive cycles, obvious CeFeO3 phase was detected, which may be responsible for favorable successive redox cycle performances.
基金Project supported by National Natural Science Foundation of China (20773090, 20803049)the Specialized Research Fund for the Doctoral Program of Higher Education (20070610026, 200806100009)
摘要Ce-Zr-Al-Nd2O3 (CZAN) support materials were prepared by co-precipitation and impregnation methods, respectively. They were characterized by X-ray diffTaction (XRD), low temperature nitrogen adsorption-desorption, oxygen pulsing technique, H2-temperamre programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS). The Pd-only three-way catalysts (Pd-TWC) supported on these materials were prepared by incipient wetness method and studied by activity tests. The results demonstrated that the CZAN supports obtained by the two methods showed better structural, textural and redox properties than the CZA without Nd2O3, and the addition of Nd203 improved the catalytic activity of TWC. Especially, the CZAN-i support prepared by impregnation method had better thermal stability and redox property. Meanwhile, the Pd/CZAN-i catalyst exhibited the best catalytic performance. XPS measurements indicated that the Nd-modified samples possessed more Ce3+ and oxygen vacancies on the surface of samples, which led to a better redox property. The excellent redox property of support materials helped to improve the catalytic activity of TWC.
基金Project supported by State Key Fundamental Research Project(G1999022400)
摘要Nickel catalysts supported on CeO2-ZrO2-CeO2,ZrO2-Al2O3 and Al2O3 were prepared and characterized by means of X-ray diffraction(XRD),BET areas,H2 temperature-programmed reduction(H2-TPR),and X-ray photoelectron spectroscopy(XPS).Through the test of catalytic partial oxidation of methane(CPOM),Ni/CeO2-ZrO2-Al2O3 displayed the highest activity,which resulted from its largest BET area and best NiO dispersion.Furthermore,Ni/CeO2-ZrO2-Al2O3 maintained a long-time stability in CPOM,which was attributed to its best coking resistance among all the prepared catalysts.
基金Project supported by the National High Technology Research and Development Program of China (863 Program,2006AA06Z347)the Specialized Research Fund for the Doctoral Program of Higher Education (20070610026)
摘要The Pd-only catalysts for motorcycle were prepared by impregnating CeO2-ZrO2-Al2O3 and CeO2-ZrO2+Al2O3 with PdCl2 aqueous solution and characterized by X-ray diffraction (XRD), oxygen storage capacity (OSC) and H2-temperature-programmed reduction (H2-TPR) methods. The XRD result indicated that the CeO2-ZrO2-Al2O3 compound prepared by co-precipitation formed a single solid solution and had good thermal stability, and Pd phase was not observed in all catalysts. The TPR results showed that the reduction temperature of Pd/CeO2-ZrO2-Al2O3 catalyst was lower than that of Pd/CeO2-ZrO2+Al2O3 catalyst whether they were fresh or aged catalysts. The Pd/CeO2-ZrO2-Al2O3 exhibited high three-way catalytic activity at low temperature, high thermal stability, and wide working window, suggesting a great potential for applications.
基金supported by the National Natural Science Foundation of China(21173153)National Hi-tech Research and Development Program of China(863)(2015AA034603)Opening Project of Key Laboratory of Green Chemistry of Sichuan Institutes of Higher Education,China(LYJ1407)~~
基金National Natural Science Foundation of China(20976120)the Natural Science Foundation of Tianjin(09JCYBJC06200)
摘要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 uptakeelease 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.