The Ce0.7Zr0.3O2 solid solution and CeO2 were prepared using the sol-gel method. The phase structure, crystallite sizes and the reducibility of the catalysts were characterized by XRD and H2-TPR techniques. XRD result...The Ce0.7Zr0.3O2 solid solution and CeO2 were prepared using the sol-gel method. The phase structure, crystallite sizes and the reducibility of the catalysts were characterized by XRD and H2-TPR techniques. XRD results indicated that Zr^4+ had replaced part of Ce^4+ to form a fluorite-like solid solution, which was favorable to obtain ultrafine nanoparticles. The ratio of main HE consumption for Ce0.7Zr0.3O2:CeO2 was 4.4:1.0, implying that the solid solution could improve the reducibility compared to the single CeO2. The Ce0.7Zr0.3O2 solid solution catalyst showed a sharp combustion peak at 397 ℃, which was 200 ℃ lower than that of the single soot. The good catalytic activity of the Ce0.7Zr0.3O2 was attributed to the formation of nano-CeO2-based solid solution, which enhanced the reducibility and then improved the combustion activity. As Ce0.7Zr0.3O2 could be easily reduced to Ce0.7Zr0.3O2-x meanwhile, after oxygenation, the Ce0.7Zr0.3O2.x was recovered to Ce0.7Zr0.3O2 completely. A catalytic combustion reaction mechanism was proposed: the Ce0.7Zr0.3O2 was reduced to Ce0.7Zr0.3O2-x by the reaction with carbon and then it was recovered to Ce0.7Zr0.3O2-x by the interaction with O2.展开更多
Layered F-doped cathode materials 0.3 Li_2 MnO_3-0.7 LiMn1/3Ni1/3CO1/3)O2-xF_x(x = 0, 0.01, 0.02, 0.03, 0.04,0.05) microspheres made up of nanosized primary grains were prepared through co-precipitation me...Layered F-doped cathode materials 0.3 Li_2 MnO_3-0.7 LiMn1/3Ni1/3CO1/3)O2-xF_x(x = 0, 0.01, 0.02, 0.03, 0.04,0.05) microspheres made up of nanosized primary grains were prepared through co-precipitation method. The sample of x = 0.02 demonstrates a large discharge capacity of226 mAh g-1 over 100 cycles at 0.1 C and excellent rate performance with discharge capacity of 96 mAh g-1 at 5.0 C and room temperature. Particularly, this material shows much enhanced electrochemical performances even at high temperature of 55 ℃. It delivers a quite high discharge capacity of 233.7 mAh·g-1 at 1.0 C with capacity retention as high as 97.9% after 100 cycles. The results demonstrate that the fluorine incorporation stabilizes the cathode structure and maintains stable interfacial resistances.展开更多
Fine grains and slow grain growth rate are beneficial to preventing the thermal stress-induced cracking and thermal conductivity increase of thermal barrier coatings.Inspired by the sluggish diffusion effect of high-e...Fine grains and slow grain growth rate are beneficial to preventing the thermal stress-induced cracking and thermal conductivity increase of thermal barrier coatings.Inspired by the sluggish diffusion effect of high-entropy materials,a novel high-entropy(HE)rare-earth zirconate solid solution(La0.2Ce0.2Nd0.2Sm0.2Eu0.2)2 Zr2 O7 was designed and successfully synthesized in this work.The as-synthesized(La0.2Ce0.2Nd0.2Sm0.2Eu0.2)2 Zr2 O7 is phase-pure with homogeneous rare-earth element distribution.The thermal conductivity of as-synthesized(La0.2Ce0.2Nd0.2Sm0.2Eu0.2)2 Zr2 O7 at room temperature is as low as 0.76 W m^-1 K^-1.Moreover,after being heated at 1500℃for 1-18 h,the average grain size of(La0.2Ce0.2Nd0.2Sm0.2Eu0.2)2 Zr2 O7 only increases from 1.69μm to 3.92μm,while the average grain size of La2Zr2O7 increases from 1.96μm to 8.89μm.Low thermal conductivity and sluggish grain growth rate indicate that high-entropy(La0.2Ce0.2Nd0.2Sm0.2Eu0.2)2Zr2O7 is suitable for application as a thermal barrier coating material and it may possess good thermal stress-induced cracking resistance.展开更多
Perovskite-type oxides La0.7Ce0.3Ni0.7Fe0.3O_3(LCNF) were synthesized by polystyrene colloidal crystal templating(LCNF-CCT) and polystyrene polymer templating(LCNF-PS) through co-precipitation. The structu...Perovskite-type oxides La0.7Ce0.3Ni0.7Fe0.3O_3(LCNF) were synthesized by polystyrene colloidal crystal templating(LCNF-CCT) and polystyrene polymer templating(LCNF-PS) through co-precipitation. The structure and physicochemical properties of the obtained oxides were investigated by scanning electron microscopy, X-ray diffraction, N_2 adsorption-desorption, Fourier transform infrared spectrometry, H_2 temperature-programmed reduction and H_2 temperature-programmed desorption, as well as X-ray photoelectron spectroscopy. The results show that the as-synthesized LCNF-CCT perovskite possesses large specific surface area and regular pore size distribution. In addition, the formation of additional oxygen vacancies on the surface favors the migration of lattice oxygen from the bulk phase to the surface and production of more metallic sites, thus improving the activity and resistance to carbon deposition of catalysts in ethanol steam reforming reaction.展开更多
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 ...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
The effect of H2O2 on the properties of Ce0.65Zr0.35O2 a mixed aqueous solution of ammonia and was explored by treating cerium nitrate and zirconium nitrate with in the presence/absence of H2O2. The resultant products...The effect of H2O2 on the properties of Ce0.65Zr0.35O2 a mixed aqueous solution of ammonia and was explored by treating cerium nitrate and zirconium nitrate with in the presence/absence of H2O2. The resultant products were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption/desorption, oxygen storage capacity (OSC) and H2- reduction (H2-TPR). The presence of H2O2 was found to have profound effect on powder properties such as surface area, crystallite size of the samples. It was also shown that the addition of H2O2 favored the incorporation of Zr4+ into CeO2 lattice, which facilitated the formation of CeO2-ZrO2 solid solution, and enhanced the thermal stability of the samples. OSC and H2-TPR studies indicated that the use of H2O2 enhanced the OSC and redox properties. Catalytic activity tests showed that as a support, the Ce0.65Zr0.35O2 prepared in the presence of H2O2 was more suitable for three-way catalyst. The corresponding Pd-only three-way catalyst demonstrated outstanding performance: wide air to fuel operation window, low light-off and total conversion temperature for the conversion of C3H8, NO and CO.展开更多
A series of Ceo.sFeo.30Zr0.20O2 catalysts were prepared by different methods (co-precipitations method, citric acid sol-gel method, impregnation method, physical mixed method, and hydrotherrnal method) and character...A series of Ceo.sFeo.30Zr0.20O2 catalysts were prepared by different methods (co-precipitations method, citric acid sol-gel method, impregnation method, physical mixed method, and hydrotherrnal method) and characterized by X-ray diffraction (XRD), Raman spectroscopy, Brunauer-Emmett-Teller (BET) and H2-TPR measurements. Potential of the catalysts in the soot oxidation was evaluated in a temperature-programmed oxidation (TPO) apparatus. The results showed that all the Fe3+ and Zr4+ were incor- porated into ceria lattice to form a pure Ce-Fe-Zr-O solid solution for the co-precipitation sample, but two kinds of Fe phases ex- isted in the Ce-Fe-Zr-O catalysts prepared by other methods: Fe3+ incorporated into CeO2 lattice and dispersed Fe2O3 clusters. The free Fe2O3 clusters could improve the activity of catalysts for soot oxidation comparing with the pure Ce-Fe-Zr-O solid solution owing to the synergetic effect between free Fe2O3 and surface oxygen vacancies. In addition, the activity of catalysts strongly relied on the surface reducibility of free Fe2O3 particles. Holding both abundant free Fe2O3 particles and high oxygen vacancy concentration, the hydrothermal Ce0.5Fe0.3Zr0.202 catalyst presented the lowest Ti (251℃, ignition temperature of soot oxidation) and Tm (310 ℃, maximum oxidation rate temperature) for soot combustion (with tight-contact between soot and catalysts) among the five samples. Even after aging at 800 ℃ for 10 h, the Ti and Tm were still relatively low, at 273 and 361 ℃, respectively, indicating high catalytic stability.展开更多
Ce0.65Zr0.35O2 solid solution was prepared by co-precipitation method and characterized by X-ray diffraction (XRD), Raman spectra, BET, oxygen storage capacity (OSC) and temperature-programmed reduction measurements (...Ce0.65Zr0.35O2 solid solution was prepared by co-precipitation method and characterized by X-ray diffraction (XRD), Raman spectra, BET, oxygen storage capacity (OSC) and temperature-programmed reduction measurements (H2-TPR) after calcination at 100 ℃, 300 ℃, 600 ℃, and 1 000 ℃. The results showed that the precipitation was a crystalline of fluorite structure, and in the process of the precipitation transformation into Ce0.65Zr0.35O2 solid solution, the fluorite structure of the precipitation kept unchanged. The samples had different BET surface areas and OSC at different temperatures, but they held the performance of stable structure. After 1 000 ℃, there didn′t appear the other crystalline phase. So the samples prepared by co-precipitation method had excellent texture and higher thermal stability.展开更多
基金the Natural Science Foundation of Zhejiang Province (Z404383)
摘要The Ce0.7Zr0.3O2 solid solution and CeO2 were prepared using the sol-gel method. The phase structure, crystallite sizes and the reducibility of the catalysts were characterized by XRD and H2-TPR techniques. XRD results indicated that Zr^4+ had replaced part of Ce^4+ to form a fluorite-like solid solution, which was favorable to obtain ultrafine nanoparticles. The ratio of main HE consumption for Ce0.7Zr0.3O2:CeO2 was 4.4:1.0, implying that the solid solution could improve the reducibility compared to the single CeO2. The Ce0.7Zr0.3O2 solid solution catalyst showed a sharp combustion peak at 397 ℃, which was 200 ℃ lower than that of the single soot. The good catalytic activity of the Ce0.7Zr0.3O2 was attributed to the formation of nano-CeO2-based solid solution, which enhanced the reducibility and then improved the combustion activity. As Ce0.7Zr0.3O2 could be easily reduced to Ce0.7Zr0.3O2-x meanwhile, after oxygenation, the Ce0.7Zr0.3O2.x was recovered to Ce0.7Zr0.3O2 completely. A catalytic combustion reaction mechanism was proposed: the Ce0.7Zr0.3O2 was reduced to Ce0.7Zr0.3O2-x by the reaction with carbon and then it was recovered to Ce0.7Zr0.3O2-x by the interaction with O2.
基金financially supported by the National Natural Science Foundation of China (No. 51372136)the NSFC-Guangdong United Fund (No. U1401246)
摘要Layered F-doped cathode materials 0.3 Li_2 MnO_3-0.7 LiMn1/3Ni1/3CO1/3)O2-xF_x(x = 0, 0.01, 0.02, 0.03, 0.04,0.05) microspheres made up of nanosized primary grains were prepared through co-precipitation method. The sample of x = 0.02 demonstrates a large discharge capacity of226 mAh g-1 over 100 cycles at 0.1 C and excellent rate performance with discharge capacity of 96 mAh g-1 at 5.0 C and room temperature. Particularly, this material shows much enhanced electrochemical performances even at high temperature of 55 ℃. It delivers a quite high discharge capacity of 233.7 mAh·g-1 at 1.0 C with capacity retention as high as 97.9% after 100 cycles. The results demonstrate that the fluorine incorporation stabilizes the cathode structure and maintains stable interfacial resistances.
基金financially supported by the National Natural Science Foundation of China (Nos.51672064 and U1435206)
摘要Fine grains and slow grain growth rate are beneficial to preventing the thermal stress-induced cracking and thermal conductivity increase of thermal barrier coatings.Inspired by the sluggish diffusion effect of high-entropy materials,a novel high-entropy(HE)rare-earth zirconate solid solution(La0.2Ce0.2Nd0.2Sm0.2Eu0.2)2 Zr2 O7 was designed and successfully synthesized in this work.The as-synthesized(La0.2Ce0.2Nd0.2Sm0.2Eu0.2)2 Zr2 O7 is phase-pure with homogeneous rare-earth element distribution.The thermal conductivity of as-synthesized(La0.2Ce0.2Nd0.2Sm0.2Eu0.2)2 Zr2 O7 at room temperature is as low as 0.76 W m^-1 K^-1.Moreover,after being heated at 1500℃for 1-18 h,the average grain size of(La0.2Ce0.2Nd0.2Sm0.2Eu0.2)2 Zr2 O7 only increases from 1.69μm to 3.92μm,while the average grain size of La2Zr2O7 increases from 1.96μm to 8.89μm.Low thermal conductivity and sluggish grain growth rate indicate that high-entropy(La0.2Ce0.2Nd0.2Sm0.2Eu0.2)2Zr2O7 is suitable for application as a thermal barrier coating material and it may possess good thermal stress-induced cracking resistance.
基金Project supported by Ordinary University Major Project of Guangdong Province,China,(2017KZDXM057)Ordinary University Characteristic Innovation Project of Guangdong Province,China,(2016KTSCX091)
摘要Perovskite-type oxides La0.7Ce0.3Ni0.7Fe0.3O_3(LCNF) were synthesized by polystyrene colloidal crystal templating(LCNF-CCT) and polystyrene polymer templating(LCNF-PS) through co-precipitation. The structure and physicochemical properties of the obtained oxides were investigated by scanning electron microscopy, X-ray diffraction, N_2 adsorption-desorption, Fourier transform infrared spectrometry, H_2 temperature-programmed reduction and H_2 temperature-programmed desorption, as well as X-ray photoelectron spectroscopy. The results show that the as-synthesized LCNF-CCT perovskite possesses large specific surface area and regular pore size distribution. In addition, the formation of additional oxygen vacancies on the surface favors the migration of lattice oxygen from the bulk phase to the surface and production of more metallic sites, thus improving the activity and resistance to carbon deposition of catalysts in ethanol steam reforming reaction.
摘要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).
基金supported by National Natural Science Foundation of China(21173153)Foundation of Science and Technology of Sichuan Province(2011GZ0035)Foundation of Environmental Protection of Sichuan Province(2011HB002)
摘要The effect of H2O2 on the properties of Ce0.65Zr0.35O2 a mixed aqueous solution of ammonia and was explored by treating cerium nitrate and zirconium nitrate with in the presence/absence of H2O2. The resultant products were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption/desorption, oxygen storage capacity (OSC) and H2- reduction (H2-TPR). The presence of H2O2 was found to have profound effect on powder properties such as surface area, crystallite size of the samples. It was also shown that the addition of H2O2 favored the incorporation of Zr4+ into CeO2 lattice, which facilitated the formation of CeO2-ZrO2 solid solution, and enhanced the thermal stability of the samples. OSC and H2-TPR studies indicated that the use of H2O2 enhanced the OSC and redox properties. Catalytic activity tests showed that as a support, the Ce0.65Zr0.35O2 prepared in the presence of H2O2 was more suitable for three-way catalyst. The corresponding Pd-only three-way catalyst demonstrated outstanding performance: wide air to fuel operation window, low light-off and total conversion temperature for the conversion of C3H8, NO and CO.
基金Project supported by National Natural Science Foundation of China(51374004,51204083,51174105,51104074)Natural Science Foundation of Yunnan Province(2010ZC018)
摘要A series of Ceo.sFeo.30Zr0.20O2 catalysts were prepared by different methods (co-precipitations method, citric acid sol-gel method, impregnation method, physical mixed method, and hydrotherrnal method) and characterized by X-ray diffraction (XRD), Raman spectroscopy, Brunauer-Emmett-Teller (BET) and H2-TPR measurements. Potential of the catalysts in the soot oxidation was evaluated in a temperature-programmed oxidation (TPO) apparatus. The results showed that all the Fe3+ and Zr4+ were incor- porated into ceria lattice to form a pure Ce-Fe-Zr-O solid solution for the co-precipitation sample, but two kinds of Fe phases ex- isted in the Ce-Fe-Zr-O catalysts prepared by other methods: Fe3+ incorporated into CeO2 lattice and dispersed Fe2O3 clusters. The free Fe2O3 clusters could improve the activity of catalysts for soot oxidation comparing with the pure Ce-Fe-Zr-O solid solution owing to the synergetic effect between free Fe2O3 and surface oxygen vacancies. In addition, the activity of catalysts strongly relied on the surface reducibility of free Fe2O3 particles. Holding both abundant free Fe2O3 particles and high oxygen vacancy concentration, the hydrothermal Ce0.5Fe0.3Zr0.202 catalyst presented the lowest Ti (251℃, ignition temperature of soot oxidation) and Tm (310 ℃, maximum oxidation rate temperature) for soot combustion (with tight-contact between soot and catalysts) among the five samples. Even after aging at 800 ℃ for 10 h, the Ti and Tm were still relatively low, at 273 and 361 ℃, respectively, indicating high catalytic stability.
摘要Ce0.65Zr0.35O2 solid solution was prepared by co-precipitation method and characterized by X-ray diffraction (XRD), Raman spectra, BET, oxygen storage capacity (OSC) and temperature-programmed reduction measurements (H2-TPR) after calcination at 100 ℃, 300 ℃, 600 ℃, and 1 000 ℃. The results showed that the precipitation was a crystalline of fluorite structure, and in the process of the precipitation transformation into Ce0.65Zr0.35O2 solid solution, the fluorite structure of the precipitation kept unchanged. The samples had different BET surface areas and OSC at different temperatures, but they held the performance of stable structure. After 1 000 ℃, there didn′t appear the other crystalline phase. So the samples prepared by co-precipitation method had excellent texture and higher thermal stability.