Thermal prehistory,structure and high-temperature thermodynamic properties of Y2O3-CeO2 and Y2O3-ZrO2-CeO2 solid solutions

Ceria-based solid solutions are important materials for high- and medium-temperature electrochemical applications. However, the stabilities of both binary and ternary ceria-based solid solutions are insufficient at elevated temperatures, which limits their application as solid electrolytes or SOFC cathodes. Data on the high-temperature stability of ceria-based ceramics are unavailable in the literature. In the present study, we report a thermodynamic stability investigation of Y₂O₃-CeO₂ and Y₂O₃-ZrO₂-CeO₂ solid solutions. The thermal prehistories of binary and ternary systems were investigated using STA, XRD, and ESCA techniques. The vaporization processes were investigated in the temperature range of 1577–2227°С via the Knudsen effusion mass spectrometry technique. Using data on the component activity in solid-phase thermodynamic properties of Y₂O₃-CeO₂ solid solutions, which is represented as the Gibbs energy, the excess Gibbs energy was calculated as a function of the ceria mol. %. It was shown that the reduction of Ce⁴⁺ to Ce³⁺ in Y₂O₃-CeO₂ and Y₂O₃-ZrO₂-CeO₂ solid solutions corresponds to less-negative Gibbs energy compared to ZrO₂-CeO₂ solid solutions.     

Stable NiO–CeO2 nanoparticles with improved carbon resistance for methane dry reforming

High surface area mixed oxide 8.7% NiO-CeO₂ nanoparticles (122 m²/g; 6–7 nm) were prepared using a reversed microemulsion method, and were tested for dry methane reforming (DRM). The catalytic activity of these nanoparticles remains stable under the severe conditions of DRM (700 °C), and they show better carbon resistance than conventional NiO-CeO₂ catalysts prepared without control of the size. The activity and selectivity of nanoparticles and reference catalyst are similar, but nanoparticles reduce the accumulation of carbon by 63% during the DRM tests, which is a key feature for this reaction. XPS and H₂-TPR suggest that the improved carbon resistance of the nanoparticles is due to the better interaction and cooperation between NiO and CeO₂ mixed phases. In nanoparticles, the participation of cerium cations in the redox processes taking place during DRM stabilizes cationic species of nickel. On the contrary, the catalyst prepared without control of the size suffers segregation of Ni during DRM reaction, and segregated Ni explains the higher catalytic formation of carbon.     

Catalytic performance of Co3O4/CeO2 and Co3O4/CeO2–ZrO2 composite oxides for methane combustion: Influence of catalyst pretreatment temperature and oxygen concentration in the reaction mixture

The influence of catalyst pre-treatment temperature (650 and 750 °C) and oxygen concentration (λ = 8 and 1) on the light-off temperature of methane combustion has been investigated over two composite oxides, Co₃O₄/CeO₂ and Co₃O₄/CeO₂–ZrO₂ containing 30 wt.% of Co₃O₄. The catalytic materials prepared by the co-precipitation method were calcined at 650 °C for 5 h (fresh samples); a portion of them was further treated at 750 °C for 7 h, in a furnace in static air (aged samples).

Tests of methane combustion were carried out on fresh and aged catalysts at two different WHSV values (12 000 and 60 000 mL g⁻¹ h⁻¹). The catalytic performance of Co₃O₄/CeO₂ and Co₃O₄/CeO₂–ZrO₂ were compared with those of two pure Co₃O₄ oxides, a sample obtained by the precipitation method and a commercial reference. Characterization studies by X-ray diffraction (XRD), BET and temperature-programmed reduction (TPR) show that the catalytic activity is related to the dispersion of crystalline phases, Co₃O₄/CeO₂ and Co₃O₄/CeO₂–ZrO₂ as well as to their reducibility. Particular attention was paid to the thermal stability of the Co₃O₄ phase in the temperature range of 750–800 °C, in both static (in a furnace) and dynamic conditions (continuous flow). The results indicate that the thermal stability of the phase Co₃O₄ heated up to 800 °C depends on the size of the cobalt oxide crystallites (fresh or aged samples) and on the oxygen content (excess λ = 8, stoichiometric λ = 1) in the reaction mixture. A stabilizing effect due to the presence of ceria or ceria–zirconia against Co₃O₄ decomposition into CoO was observed.

Moreover, the role of ceria and ceria–zirconia is to maintain a good combustion activity of the cobalt composite oxides by dispersing the active phase Co₃O₄ and by promoting the reduction at low temperature.     

贵金属催化净化汽车尾气中稀土氧化物的助催化和稳定化

面临日趋严格的汽车尾气排放标准，采用同时进行CO和烃类氧化，NOx还原的Pt／Rh系三效催化剂是一种有效的解决办法。在汽车污染控制中使用助催化剂CeO2，是今天稀土氧化物最重要的应用，Ce^3 ／Ce^4 在氧化／还原条件下可以贮存／释放氧，扩宽了中心接近化学计量的催化剂活性工作带，氧化铈促进反应物分子的活化而降低反应温度。当前三效催化剂中，采用CeO2－ZrO2混合氧化物反映了发展紧偶催化剂的最先进的工艺。含少量Ru、Rh、Pt等贵金属的稀土钙钛矿型氧化物有可能成实用的净化汽车尾气三效催化剂。     

Synthesis and Characterization of Sm_xGd_yCe_(1-x-y)O_(2-δ) Nanopowders

SmxGdyCe1-x-yO2-δ (x+y=0.2 and x=0, 0.04, 0.08, 0.12, 0.16, 0.2) nanopowders were prepared by a copre-cipitation method. The zeta potential and sedimentation volume of Ce(OH)4 aqueous dispersions at different pH values were measured. The isoelectric point (IEP) of Ce(OH)4 suspensions is 7.0. The maximum potential value of -18.5 mV and maximum sedimentation volume of 19 ml are reached at pH=10. The evolution behaviors of the xSm(OH)3·yGd(OH)3·(1-x-y)Ce(OH)4 dried powders in the heating process was characterized by DTA/TG and XRO. The powders decompose to ceria based solid solution at a temperature below 300℃ and forms cubic fluorite structure ceria at about 650℃. The properties of SmxGdyCe1-x-yO2-δ solid solutions were characterized by XRD, TEM and BET. The lattice parameter of doped Ce02 increases linearly with increasing Sm3+ substitution (or decreasing Gd3+ substitution). The particle size of the doped ceria powders is from 5 nm to 10 nm.     

The effects of PVP surfactant in the direct and indirect hydrothermal synthesis processes of ceria nanostructures

CeO₂ nanostructures with completely different morphologies were successfully prepared using the same cerium source and mineralizer through the direct and indirect hydrothermal methods with different introducing strategies of PVP surfactant. The CeO₂ nanostructures tend to form the morphologies of nano-flowers and nano-cubes through the indirect and direct hydrothermal methods, respectively. X-ray diffraction (XRD) analyses revealed that both as-prepared nanostructures are composed of CeO₂ with a standard fluorite structure. The different synthesis mechanisms and corresponding chemical evolutions of the as-prepared CeO₂ nanostructures are discussed based on the different introducing strategies of PVP surfactant in the direct and indirect hydrothermal processes. Investigation of the UV-shielding ability of both CeO₂ nanostructures suggested that the UV absorbance of the nano-flowers is much higher than that of the nano-cubes.     

Low temperature densification by lithium co-doping and its effect on ionic conductivity of samarium doped ceria electrolyte

Low temperature densification and improving the ionic conductivity of doped ceria electrolyte is important for the realization of efficient intermediate temperature solid oxide fuel cell system. Herein, we report the effect of lithium co-doping (1, 3, 5 and 7?mol%) in 20?mol% samarium doped ceria on the low temperature sinterability and conductivity. The synthesized nanoparticles by citrate-nitrate combustion method showed a decrease in lattice parameter and increase in oxygen vacancy with lithium content after calcination due to the substitution of Li⁺ into CeO₂ lattice. Upon sintering at 900?°C, the density improved and reached a maximum value of 98.6% for 5% Li which exhibited a dense microstructure than at 7% Li. 5%Li co-doping exhibited the best conductivity of 3.65?×?10^?04–1.81?×?10^?3 S?cm^?1 in the operative temperature range of IT-SOFC (550–700?°C).Our results demonstrate the significance of lithium as co-dopant for efficient low temperature sintering as well as improving the electrolyte conductivity.     

Gd-Bi-M-Ce-O (M = Cu,Zr, Ni,Co, Mn) ceria-based solid solutions for low temperature CO oxidation

Ceria based solid solutions doped by Gd, Bi, and the third dopant were synthesized by the co-precipitation method with ultrasonic treatment, followed by calcination at the temperature of 500°С. Characterization of the synthesized nanosystems by XRD, TEM, TG, Raman spectroscopy, FTIR, XPS was carried out. It is shown that all obtained powders of solid solutions crystallized into a cubic structure of the fluorite type, with an average particle size of 5–15 nm. The samples had a mesoporous structure of the pore diameter of 2–5 nm. The catalytic activity of Gd-Bi-M-Ce-O (M = Cu, Zr, Ni, Co, Mn) solid solutions was carried out. The catalyst Gd_0.05Bi_0.15Mn_0.20Ce_0.60O₂ has the lowest oxidation temperature.     

Hierarchical,template-free self-assembly morphologies in CeO2 synthesized via urea-hydrothermal method

Nano-crystalline CeO₂ was synthesized via the urea-hydrothermal method without templates or structure-directing agents. The synthesis parameters Ce³⁺ to Ce⁴⁺ and urea to cation molar ratios, reaction temperature and reaction time were varied to analyze their effect on morphology, texture and reducibility. The analysis of the obtained morphologies provides strong evidence of a hierarchical and sequential template-free self-assembly process that evolves from shuttles to dumbbells to spheres. In all cases, the morphology of samples remains unchanged even after calcination at 500 °C. The presence of Ce⁴⁺ in the initial solution clearly provides the full self-assembly sequence and is decisive for obtaining non-hollow spheres of CeO₂ with high specific surface area and high pore volume. Besides, if only Ce³⁺ is present, typical CeOHCO₃ shuttle-like particles with orthorhombic structure are obtained. The use of Ce³⁺ in combination with Ce⁴⁺ produces partial sequences of the self-assembly process that provide a strong indication of the hierarchical sequence.The urea to cation molar ratio controls the nucleation process and proves to be crucial to obtain the self-assembly sequence. On the other hand, temperature and reaction time show a moderate effect on morphology.