Pr0.7Zr0.3O2-δ solid solution was prepared by co-precipitation method and used as an oxygen carrier in the selective oxidation of methane to syngas(methane/air redox process). The evolution on the physicochemical pro...Pr0.7Zr0.3O2-δ solid solution was prepared by co-precipitation method and used as an oxygen carrier in the selective oxidation of methane to syngas(methane/air redox process). The evolution on the physicochemical properties of Pr0.7Zr0.3O2-δ during the redox process was studied by means of X-ray diffraction(XRD), H2 temperature-programmed reduction(H2-TPR), O2temperature-programmed desorption(O2-TPD), Brunauer-Emmett-Teller(BET) surface area measurement and X-ray photoelectron spectroscopy(XPS) technologies. The results indicated that Pr0.7Zr0.3O2-δ solid solution showed the high activity for the methane conversion to syngas with a high CO selectivity in the range of 83.5%-88.1%. Though Pr-Zr solid solution possessed high thermal stability, lattice oxygen was obviously reduced for the recycled sample due to decreased surface oxygen which promoted oxygen vacancies. The increased oxygen vacancies seemed to enhance the oxygen transfer ability in the redox process and provided sufficient oxygen for the methane selective oxidation, resulting in a satisfactory activity. The problem of hot pot was avoided by comparing fresh, aged and recycle sample in the reaction.展开更多
Crystallization kinetics of Pr 8Fe 86 x Zr x B 6 ( x =0, 1, 2) amorphous alloys was studied by DTA and XRD methods. The experimental results showed that the crystalline phases of Pr 8Fe 86 B 6 ...Crystallization kinetics of Pr 8Fe 86 x Zr x B 6 ( x =0, 1, 2) amorphous alloys was studied by DTA and XRD methods. The experimental results showed that the crystalline phases of Pr 8Fe 86 B 6 alloy are composed of α Fe phase, Pr 2Fe 23 B 3 and Pr 2Fe 14 B, when crystallization temperature is below 900 ℃. The activation energy of α Fe phase remains relatively constant about 306.09 kJ/mol, as the crystalline fraction of α Fe phase is below 8 %. At the beginning of crystallization, the activation energy of Pr 2Fe 23 B 3 and Pr 2Fe 14 B phases are 510.85 kJ/mol and 725.97 kJ/mol, respectively, and then the activation energy of three phases declines with increasing the crystalline fraction. The crystallization behavior of α Fe and Pr 2Fe 14 B essentially results in the formation of a α Fe/Pr 2Fe 14 B composite microstructure with a coarse grain size in annealed Pr 8Fe 86 B 6 alloy, which is attributed to a difficult nucleation and an easy growth for both the α Fe and Pr 2Fe 14 B in the alloy. Zr can be used to change the crystallization behavior of the α Fe phase in Pr Fe B amorphous alloy, which is helpful to the formation of the α Fe/Pr 2Fe 14 B nanocomposite microstructure with a fine grain size for the α Fe phase in the alloy.展开更多
The effects of Zr on crystallization kinetics of Pr Fe B amorphous alloys have been investigated by DTA and XRD methods. It was found that for Pr 8Fe 86- x Zr x B 6 ( x =0, 1, 2) amorphous alloys, the final crystalliz...The effects of Zr on crystallization kinetics of Pr Fe B amorphous alloys have been investigated by DTA and XRD methods. It was found that for Pr 8Fe 86- x Zr x B 6 ( x =0, 1, 2) amorphous alloys, the final crystallized mixture is α Fe and Pr 2Fe 14 B, and the metastable Pr 2Fe 23 B 3 phase occurs during crystallization of Pr 8Fe 86 B 6 amorphous alloy, not during crystallization of Pr 8Fe 86- x Zr x B 6( x =1, 2) amorphous alloys. By analyzing the activation energy of crystallization, the formation of an α Fe/Pr 2Fe 14 B composite microstructure with a coarse grain size in annealed Pr 8Fe 86 B 6 alloy, is attributed to a difficult nucleation and an easy growth for both the α Fe and Pr 2Fe 14 B in the alloy. The addition of Zr can be used to change the crystallization behavior of the α Fe phase in Pr Fe B amorphous alloy, which is helpful to reduce the grain size for the α Fe phase.展开更多
A series of catalysts with (Ce-Zr-La-Pr)O contents range from 0 to 50% in coating and single-palladium loads on substrates were prepared to study effects of (Ce-Zr-La-Pr)O contents on catalytic activities and durabili...A series of catalysts with (Ce-Zr-La-Pr)O contents range from 0 to 50% in coating and single-palladium loads on substrates were prepared to study effects of (Ce-Zr-La-Pr)O contents on catalytic activities and durability by contrasting the characteristics of light-off, A/F and catalytic conversions of the fresh catalysts with that of the aged catalysts. The results show that (Ce-Zr-La-Pr)O can enhance the catalysts light-off characteristics, widen A/F windows and increase catalytic conversions at a certain extent through optimizing physical structural and chemical property of the mixed coating. However, (Ce-Zr-La-Pr)O contents influence greatly on the catalysts activities and durability, and the catalysts with contents ranging from 10% to 30% exhibited better integrative properties in all samples, and 10% was the optical content to make the catalyst performance highest in this thesis. It is indicated that an suitable content of (Ce-Zr-La-Pr)O plays an important role in assisting catalysis, enhancing durability and increasing oxygen storage capability.展开更多
Important effects exist between precious metals and rare earths oxides in three-way catalyst, especially the coordinated effects. These effects were studied by using H2PtCl6, Pt(NH3)2(NO2)2 and Pt(OH)2(C2H5ONH2)2 as P...Important effects exist between precious metals and rare earths oxides in three-way catalyst, especially the coordinated effects. These effects were studied by using H2PtCl6, Pt(NH3)2(NO2)2 and Pt(OH)2(C2H5ONH2)2 as Pt precursors, and the mixed oxide of (Ce-Zr-La-Pr)O as base material to prepare a series of catalysts, and their performances of the catalysts were studied by TPR and CO pulse titration technologies. The results shown that Pt precursors and their solutions pH values influenced the oxygen storage capabilities, the active metal distribution degrees of the catalysts obviously, and every catalyst prepared by different precursors had an optimal pH values. It indicates that the active metals precursors and their solutions acidities have outstanding influences on the catalysts performances for the mutual effects existing between the active metals and the Rare Earth metal oxides, which results from the mate groups of the precursors and the solution acidity.展开更多
For nanophase (Nd, Pr)FeB/α-Fe composite alloys were prepared by melt spinning, the appreciable addition of Zr reduces their average grain size. Observed by atom force microscopy (AFM), the average grain diameter of ...For nanophase (Nd, Pr)FeB/α-Fe composite alloys were prepared by melt spinning, the appreciable addition of Zr reduces their average grain size. Observed by atom force microscopy (AFM), the average grain diameter of crystallized ribbons on their free surface, reduces from 175 nm of Zr-free alloy to 79 nm of Zr-1at%, by about 55%. If the concentration exceeds 1%, the effects of Zr on fining grain size are evidently weakened. The average grain size on free surface of Zr-1.5at% is 72 nm. With the addition of 1at% Zn, the bonded magnets has the best combination of properties: B_r=0.675 T, H_(ci)=616 kA·m^(-1), (BH)_(max)=77 kJ·m^(-3). Below 1at%, the coarser grains lead to a lower magnetic property. Beyond 1at%, the layer of Zr-rich intergranular phase will thicken, which results in weakening of the exchange coupling among adjacent grains, and then causes degrading of magnetic properties of magnets.展开更多
基金supported by the National Natural Science Foundation of China(51568068)the Young and Middle-aged Academic and Technical Leaders Reserve Talent Project(202105AC160054).
基金Projects(51374004,51174105,51204083,51104074,51306084)supported by the National Natural Science Foundation of ChinaProjects(2012FD016,2014HB006)supported by the Applied Basic Research Program of Yunnan Province,ChinaProject(2010241)supported by the Analysis and Testing Foundation of Kunming University of Science and Technology,China
文摘Pr0.7Zr0.3O2-δ solid solution was prepared by co-precipitation method and used as an oxygen carrier in the selective oxidation of methane to syngas(methane/air redox process). The evolution on the physicochemical properties of Pr0.7Zr0.3O2-δ during the redox process was studied by means of X-ray diffraction(XRD), H2 temperature-programmed reduction(H2-TPR), O2temperature-programmed desorption(O2-TPD), Brunauer-Emmett-Teller(BET) surface area measurement and X-ray photoelectron spectroscopy(XPS) technologies. The results indicated that Pr0.7Zr0.3O2-δ solid solution showed the high activity for the methane conversion to syngas with a high CO selectivity in the range of 83.5%-88.1%. Though Pr-Zr solid solution possessed high thermal stability, lattice oxygen was obviously reduced for the recycled sample due to decreased surface oxygen which promoted oxygen vacancies. The increased oxygen vacancies seemed to enhance the oxygen transfer ability in the redox process and provided sufficient oxygen for the methane selective oxidation, resulting in a satisfactory activity. The problem of hot pot was avoided by comparing fresh, aged and recycle sample in the reaction.
文摘Crystallization kinetics of Pr 8Fe 86 x Zr x B 6 ( x =0, 1, 2) amorphous alloys was studied by DTA and XRD methods. The experimental results showed that the crystalline phases of Pr 8Fe 86 B 6 alloy are composed of α Fe phase, Pr 2Fe 23 B 3 and Pr 2Fe 14 B, when crystallization temperature is below 900 ℃. The activation energy of α Fe phase remains relatively constant about 306.09 kJ/mol, as the crystalline fraction of α Fe phase is below 8 %. At the beginning of crystallization, the activation energy of Pr 2Fe 23 B 3 and Pr 2Fe 14 B phases are 510.85 kJ/mol and 725.97 kJ/mol, respectively, and then the activation energy of three phases declines with increasing the crystalline fraction. The crystallization behavior of α Fe and Pr 2Fe 14 B essentially results in the formation of a α Fe/Pr 2Fe 14 B composite microstructure with a coarse grain size in annealed Pr 8Fe 86 B 6 alloy, which is attributed to a difficult nucleation and an easy growth for both the α Fe and Pr 2Fe 14 B in the alloy. Zr can be used to change the crystallization behavior of the α Fe phase in Pr Fe B amorphous alloy, which is helpful to the formation of the α Fe/Pr 2Fe 14 B nanocomposite microstructure with a fine grain size for the α Fe phase in the alloy.
文摘The effects of Zr on crystallization kinetics of Pr Fe B amorphous alloys have been investigated by DTA and XRD methods. It was found that for Pr 8Fe 86- x Zr x B 6 ( x =0, 1, 2) amorphous alloys, the final crystallized mixture is α Fe and Pr 2Fe 14 B, and the metastable Pr 2Fe 23 B 3 phase occurs during crystallization of Pr 8Fe 86 B 6 amorphous alloy, not during crystallization of Pr 8Fe 86- x Zr x B 6( x =1, 2) amorphous alloys. By analyzing the activation energy of crystallization, the formation of an α Fe/Pr 2Fe 14 B composite microstructure with a coarse grain size in annealed Pr 8Fe 86 B 6 alloy, is attributed to a difficult nucleation and an easy growth for both the α Fe and Pr 2Fe 14 B in the alloy. The addition of Zr can be used to change the crystallization behavior of the α Fe phase in Pr Fe B amorphous alloy, which is helpful to reduce the grain size for the α Fe phase.
文摘A series of catalysts with (Ce-Zr-La-Pr)O contents range from 0 to 50% in coating and single-palladium loads on substrates were prepared to study effects of (Ce-Zr-La-Pr)O contents on catalytic activities and durability by contrasting the characteristics of light-off, A/F and catalytic conversions of the fresh catalysts with that of the aged catalysts. The results show that (Ce-Zr-La-Pr)O can enhance the catalysts light-off characteristics, widen A/F windows and increase catalytic conversions at a certain extent through optimizing physical structural and chemical property of the mixed coating. However, (Ce-Zr-La-Pr)O contents influence greatly on the catalysts activities and durability, and the catalysts with contents ranging from 10% to 30% exhibited better integrative properties in all samples, and 10% was the optical content to make the catalyst performance highest in this thesis. It is indicated that an suitable content of (Ce-Zr-La-Pr)O plays an important role in assisting catalysis, enhancing durability and increasing oxygen storage capability.
基金Project supported by the National High Technology Research and Development Programs (863 ) of China (2002 AA321060, 2004AA649040) Yunnan Province Science Technology Program (2004B0028Q)
文摘Important effects exist between precious metals and rare earths oxides in three-way catalyst, especially the coordinated effects. These effects were studied by using H2PtCl6, Pt(NH3)2(NO2)2 and Pt(OH)2(C2H5ONH2)2 as Pt precursors, and the mixed oxide of (Ce-Zr-La-Pr)O as base material to prepare a series of catalysts, and their performances of the catalysts were studied by TPR and CO pulse titration technologies. The results shown that Pt precursors and their solutions pH values influenced the oxygen storage capabilities, the active metal distribution degrees of the catalysts obviously, and every catalyst prepared by different precursors had an optimal pH values. It indicates that the active metals precursors and their solutions acidities have outstanding influences on the catalysts performances for the mutual effects existing between the active metals and the Rare Earth metal oxides, which results from the mate groups of the precursors and the solution acidity.
文摘For nanophase (Nd, Pr)FeB/α-Fe composite alloys were prepared by melt spinning, the appreciable addition of Zr reduces their average grain size. Observed by atom force microscopy (AFM), the average grain diameter of crystallized ribbons on their free surface, reduces from 175 nm of Zr-free alloy to 79 nm of Zr-1at%, by about 55%. If the concentration exceeds 1%, the effects of Zr on fining grain size are evidently weakened. The average grain size on free surface of Zr-1.5at% is 72 nm. With the addition of 1at% Zn, the bonded magnets has the best combination of properties: B_r=0.675 T, H_(ci)=616 kA·m^(-1), (BH)_(max)=77 kJ·m^(-3). Below 1at%, the coarser grains lead to a lower magnetic property. Beyond 1at%, the layer of Zr-rich intergranular phase will thicken, which results in weakening of the exchange coupling among adjacent grains, and then causes degrading of magnetic properties of magnets.