The three way catalysts (TWCs) promoters (Ce Zr)O 2, (Pr Ce Zr)O 2 and (Pr Zr)O 2 were prepared by sol gel like method. They were characterized by XRD, EXAFS and BET surface area determination. The reduction ...The three way catalysts (TWCs) promoters (Ce Zr)O 2, (Pr Ce Zr)O 2 and (Pr Zr)O 2 were prepared by sol gel like method. They were characterized by XRD, EXAFS and BET surface area determination. The reduction features of the promoters were measured by temperature programmed reduction (TPR) of H 2 to access the potential for the promoters containing praseodymia as oxygen storage component in three way catalyst. The (Pr Zr)O 2 cubic solid solution is formed at high temperature up to 800 ℃, which makes it more reducible than the (Ce Zr)O 2 solid solution. For the (Pr Ce Zr)O 2 samples, the ternary solid solution plays an important role in the reduction process. The performance of the three way catalysts with fully formulated Pt, Pd and Rh is proceeded by using both light off temperature under a stoichiometric gas composition and the conversion of CO, C 3H 6 and NO under changing air/fuel ratio at a constant reaction temperature 400 ℃ . The results indicate that a small amount of praseodymia doping into (Ce Zr)O 2 favors the light off temperature of C 3H 6 and NO, and all the catalysts containing praseodymia obviously exhibits enhanced width of S value for NO conversion at lean region ( S ≥1.00).展开更多
Ce Zr O solid solution was prepared by four different methods, i.e., decomposition of nitrate, coprecipiation, hydroxysuainic acid sol gel as well as citrate sol gel, and characterized by using X ray powder diffr...Ce Zr O solid solution was prepared by four different methods, i.e., decomposition of nitrate, coprecipiation, hydroxysuainic acid sol gel as well as citrate sol gel, and characterized by using X ray powder diffraction, Raman and temperature programmed reduction. The phase composition and the reduction properties of Ce Zr O depend on the preparation method. A cubic Ce 0.5 Zr 0.5 O 2 solid solution can be obtained by using the sol gel method. The Ce Zr O solid solution prepared by using decomposition or coprecipiation was composed of cubic Ce 0.8 Zr 0.2 O 2 and tetragonal Ce 0.2 Zr 0.8 O 2 solid solution. The Ce Zr O solid solution prepared with different methods shows the different reduction properties owing to different phase composition. Results of differential thermal analysis and XRD show that Ce 0.5 Zr 0.5 O 2 solid solution is formed during the decomposition or combustion of the gel.展开更多
The three-way catalysts (TWCs) promoters Ce0.6Zr0.4- x TbxO2-y were prepared by sol-gel method. BET surface areas analysis indicated that an increase of the dopant Tb content from x = 0.05 to x = 0.15 favors an incr...The three-way catalysts (TWCs) promoters Ce0.6Zr0.4- x TbxO2-y were prepared by sol-gel method. BET surface areas analysis indicated that an increase of the dopant Tb content from x = 0.05 to x = 0.15 favors an increase of surface area from 66.8 to 80.4 m^2· g^-1 compared with the undoped sample Ce0 .6oZr0.40O2 65.1 m^2·g^- 1 after calcination at 650℃. Transmission electron microscopy (TEM) observation indicated that the doped samples have a higher thermal stability. The XRD and Raman spectra confirmed that the Ce0.6Zr0.4-xTbxO2-y cubic solid solution is formed. XPS analysis revealed that Ce and Tb mainly existed in the form of Ce^4+ and Tb^3 + , and Zr existed in the form of Zr^4+ on the surface of the samples. The doped samples were homogenous in composition ; the introduction of Tb into the CeO2-ZrO2 promoters resuited in the formation of a solid solution, and the concentration of surface lattice oxygen was increased.展开更多
The structure and properties of Cu-Cr-Zr alloy were studied after rapidly solidified aging and solid solution aging.At the early stage of aging (500℃ for 15 rain), the hardness and the conductivity of the alloy rap...The structure and properties of Cu-Cr-Zr alloy were studied after rapidly solidified aging and solid solution aging.At the early stage of aging (500℃ for 15 rain), the hardness and the conductivity of the alloy rapidly solidified are 143 HV and 72% IACS, respectively. Under the same aging condition, the hardness and electrical conductivity of the alloy solid solution treated can reach 86 HV and 47% IACS, respectively. The microstructure was analyzed, and the grain size after rapid solidification is much smaller than that after solid solution treatment. By rapidly solidified aging the fine precipitates distribute inside the grains and along the grain boundary, while by solid solution aging there are large Cr particles along the grain boundary.展开更多
Nanosized Ce^1-x)(Nd^0.5)Eu^0.5))xO^2-δ) solid solutions(x = 0.00-0.20) were synthesized by means of hydrothermal method.Then the solid solutions were ball milled with Mg2Ni and Ni powders for 20 h to get the...Nanosized Ce^1-x)(Nd^0.5)Eu^0.5))xO^2-δ) solid solutions(x = 0.00-0.20) were synthesized by means of hydrothermal method.Then the solid solutions were ball milled with Mg2Ni and Ni powders for 20 h to get the Mg2Ni–Ni–5 mol% Ce^1-x)(Nd^0.5)Eu^0.5))xO^2-δ) composites.The structures and spectrum characteristics of the Ce^1-x)(Nd^0.5)Eu^0.5))xO^2-δ) solid solutions catalysts were analyzed systemically.XRD results showed that the doped samples exhibited single phase of CeO2 fluorite structure.The cell parameters and cell volumes were increased with increasing the doped content.Raman spectrum revealed that the peak position of F^2g mode shift to higher wavenumbers and the peak corresponding to oxygen vacancies were observed distinctly for the doped samples.UV-Vis technique indicated that the absorption peaks of Eu^3+ and Nd^3+ ions appeared; the bandgap energy was decreased linearly.The electrochemical and kinetic properties of the Mg2Ni–Ni–5 mol% Ce1-x(Nd0.5Eu0.5xO2-δ composites were measured.The maximum discharge capacity was increased from 722.3 mA h/g for x = 0.00 to 819.7 mA h/g for x = 0.16,and the cycle stability S20 increased from 25.0%(x = 0.00) to 42.2%(x = 0.20).The kinetic measurement proved that the catalytic activity of composite surfaces and the hydrogen diffusion rate were improved for the composites with doped catalysts,especially for the composites with x = 0.16 and x = 0.20.The catalysis mechanism was analyzed from the point of microstructure and spectrum features of the Ce1-x(Nd0.5Eu0.5)xO2-δ solid solutions.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
Multicomponent boron-containing carbide coatings(i.e.,(Zr,Ti)C_(x)B_(y))on a C/C composite show good ablation resistance.However,the high-temperature oxidation behavior of this new type of boron-containing(Zr,Ti)C_(x)...Multicomponent boron-containing carbide coatings(i.e.,(Zr,Ti)C_(x)B_(y))on a C/C composite show good ablation resistance.However,the high-temperature oxidation behavior of this new type of boron-containing(Zr,Ti)C_(x)B_(y)solid solution ceramics has not been clarified yet.The present work fabricated(Zr,Ti)C_(x)B_(y)solid solution block ceramics by spark plasma sintering,and their oxidation behavior at 1600℃in air(N2–20-vol%O2)was investigated for the first time.The effects of boron on the oxidation resistance of(Zr,Ti)C_(x)B_(y)ceramics were examined.The results indicate that the(Zr,Ti)C_(x)B_(y)ceramics display good oxidation resistance with the parabolic rate law describing the oxidation process.After the trace solution of boron(0.5 wt%)into(Zr,Ti)Cx,the oxidation resistance of carbide ceramics is significantly enhanced,leading to a decrease of 30%in the oxidation rate constant.The formed oxide scale in the(Zr,Ti)C_(x)B_(y)ceramics is dense,and the interlayer shows stronger ability to inhibit inward diffusion of oxygen.In addition,the introduction of boron leads to more negative binding energy of(Zr,Ti)C_(x)B_(y)and improves the oxidation resistance of carbides.展开更多
文摘The three way catalysts (TWCs) promoters (Ce Zr)O 2, (Pr Ce Zr)O 2 and (Pr Zr)O 2 were prepared by sol gel like method. They were characterized by XRD, EXAFS and BET surface area determination. The reduction features of the promoters were measured by temperature programmed reduction (TPR) of H 2 to access the potential for the promoters containing praseodymia as oxygen storage component in three way catalyst. The (Pr Zr)O 2 cubic solid solution is formed at high temperature up to 800 ℃, which makes it more reducible than the (Ce Zr)O 2 solid solution. For the (Pr Ce Zr)O 2 samples, the ternary solid solution plays an important role in the reduction process. The performance of the three way catalysts with fully formulated Pt, Pd and Rh is proceeded by using both light off temperature under a stoichiometric gas composition and the conversion of CO, C 3H 6 and NO under changing air/fuel ratio at a constant reaction temperature 400 ℃ . The results indicate that a small amount of praseodymia doping into (Ce Zr)O 2 favors the light off temperature of C 3H 6 and NO, and all the catalysts containing praseodymia obviously exhibits enhanced width of S value for NO conversion at lean region ( S ≥1.00).
文摘Ce Zr O solid solution was prepared by four different methods, i.e., decomposition of nitrate, coprecipiation, hydroxysuainic acid sol gel as well as citrate sol gel, and characterized by using X ray powder diffraction, Raman and temperature programmed reduction. The phase composition and the reduction properties of Ce Zr O depend on the preparation method. A cubic Ce 0.5 Zr 0.5 O 2 solid solution can be obtained by using the sol gel method. The Ce Zr O solid solution prepared by using decomposition or coprecipiation was composed of cubic Ce 0.8 Zr 0.2 O 2 and tetragonal Ce 0.2 Zr 0.8 O 2 solid solution. The Ce Zr O solid solution prepared with different methods shows the different reduction properties owing to different phase composition. Results of differential thermal analysis and XRD show that Ce 0.5 Zr 0.5 O 2 solid solution is formed during the decomposition or combustion of the gel.
基金Project supported by the Natural Science Basic Research Plan in Shaanxi Province of China (2004B13)
文摘The three-way catalysts (TWCs) promoters Ce0.6Zr0.4- x TbxO2-y were prepared by sol-gel method. BET surface areas analysis indicated that an increase of the dopant Tb content from x = 0.05 to x = 0.15 favors an increase of surface area from 66.8 to 80.4 m^2· g^-1 compared with the undoped sample Ce0 .6oZr0.40O2 65.1 m^2·g^- 1 after calcination at 650℃. Transmission electron microscopy (TEM) observation indicated that the doped samples have a higher thermal stability. The XRD and Raman spectra confirmed that the Ce0.6Zr0.4-xTbxO2-y cubic solid solution is formed. XPS analysis revealed that Ce and Tb mainly existed in the form of Ce^4+ and Tb^3 + , and Zr existed in the form of Zr^4+ on the surface of the samples. The doped samples were homogenous in composition ; the introduction of Tb into the CeO2-ZrO2 promoters resuited in the formation of a solid solution, and the concentration of surface lattice oxygen was increased.
基金This work was supported by the National“863”High Pro-gram of China(No.2002AA331112)the Doctorate Foun-dation of Northwestern Polytechnical University(CX200409)the Science Research Foundation of Henan University of Science and Technology(No.2004ZY039).
文摘The structure and properties of Cu-Cr-Zr alloy were studied after rapidly solidified aging and solid solution aging.At the early stage of aging (500℃ for 15 rain), the hardness and the conductivity of the alloy rapidly solidified are 143 HV and 72% IACS, respectively. Under the same aging condition, the hardness and electrical conductivity of the alloy solid solution treated can reach 86 HV and 47% IACS, respectively. The microstructure was analyzed, and the grain size after rapid solidification is much smaller than that after solid solution treatment. By rapidly solidified aging the fine precipitates distribute inside the grains and along the grain boundary, while by solid solution aging there are large Cr particles along the grain boundary.
基金supported by the National Natural Science Foundations of China(51501095,51371094)the Natural Science Foundation of Inner Mongolia(2017MS(LH)0516)
文摘Nanosized Ce^1-x)(Nd^0.5)Eu^0.5))xO^2-δ) solid solutions(x = 0.00-0.20) were synthesized by means of hydrothermal method.Then the solid solutions were ball milled with Mg2Ni and Ni powders for 20 h to get the Mg2Ni–Ni–5 mol% Ce^1-x)(Nd^0.5)Eu^0.5))xO^2-δ) composites.The structures and spectrum characteristics of the Ce^1-x)(Nd^0.5)Eu^0.5))xO^2-δ) solid solutions catalysts were analyzed systemically.XRD results showed that the doped samples exhibited single phase of CeO2 fluorite structure.The cell parameters and cell volumes were increased with increasing the doped content.Raman spectrum revealed that the peak position of F^2g mode shift to higher wavenumbers and the peak corresponding to oxygen vacancies were observed distinctly for the doped samples.UV-Vis technique indicated that the absorption peaks of Eu^3+ and Nd^3+ ions appeared; the bandgap energy was decreased linearly.The electrochemical and kinetic properties of the Mg2Ni–Ni–5 mol% Ce1-x(Nd0.5Eu0.5xO2-δ composites were measured.The maximum discharge capacity was increased from 722.3 mA h/g for x = 0.00 to 819.7 mA h/g for x = 0.16,and the cycle stability S20 increased from 25.0%(x = 0.00) to 42.2%(x = 0.20).The kinetic measurement proved that the catalytic activity of composite surfaces and the hydrogen diffusion rate were improved for the composites with doped catalysts,especially for the composites with x = 0.16 and x = 0.20.The catalysis mechanism was analyzed from the point of microstructure and spectrum features of the Ce1-x(Nd0.5Eu0.5)xO2-δ solid solutions.
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.
基金supported by the National Natural Science Foundation of China(No.5207021797)the Scientific Research and Technology Development Project of China National Petroleum Corporation Limited(No.2020E-2804(JT)).
文摘Multicomponent boron-containing carbide coatings(i.e.,(Zr,Ti)C_(x)B_(y))on a C/C composite show good ablation resistance.However,the high-temperature oxidation behavior of this new type of boron-containing(Zr,Ti)C_(x)B_(y)solid solution ceramics has not been clarified yet.The present work fabricated(Zr,Ti)C_(x)B_(y)solid solution block ceramics by spark plasma sintering,and their oxidation behavior at 1600℃in air(N2–20-vol%O2)was investigated for the first time.The effects of boron on the oxidation resistance of(Zr,Ti)C_(x)B_(y)ceramics were examined.The results indicate that the(Zr,Ti)C_(x)B_(y)ceramics display good oxidation resistance with the parabolic rate law describing the oxidation process.After the trace solution of boron(0.5 wt%)into(Zr,Ti)Cx,the oxidation resistance of carbide ceramics is significantly enhanced,leading to a decrease of 30%in the oxidation rate constant.The formed oxide scale in the(Zr,Ti)C_(x)B_(y)ceramics is dense,and the interlayer shows stronger ability to inhibit inward diffusion of oxygen.In addition,the introduction of boron leads to more negative binding energy of(Zr,Ti)C_(x)B_(y)and improves the oxidation resistance of carbides.