(Ce0.9Nd0.1)1-xMoxO2-δ(0.00≤x≤0.10)的合成、表征与电性能

采用溶胶-凝胶法合成(Ce0.9Nd0.1)1-xMoxO2-δ(x=0.00、0.02、0.05、0.10)氧化物,通过X射线衍射(XRD)、场发射扫描电镜(FESEM)等手段对氧化物进行结构表征,交流阻抗谱测试电性能.结果表明:所有样品均为单一萤石立方结构;少量MoO3的加入提高了材料的致密性,降低了材料的总电阻、晶界电阻和晶界电阻在总电阻中所占比例,提高了材料的电导率.1200 ℃烧结样品24 h,测试温度700℃时,(Ce0.9Nd0.1)1-xMoxO2-δ(x=O.00)总电导率和晶界电导率分别为0.05和O.19 S·m-1,掺Mo材料(Ce0.9Nd0.1)1-xMoxO2(x=0.02)的总电导率和晶界电导率分别为2.42和3.96 S·m-1.     

天然气中温SOFC阳极材料铒掺杂的氧化铈的制备与性能研究

采用溶胶-凝胶法合成了新型中温固体氧化物燃料电池(IT-SOFC)阳极材料Ce_1-xEr_xO_y(x=0.00,0.10,0.15,0.20,0.25,0.30)(EDC),并采用共压-共烧结法制备了以NiO-EDC复合阳极为支撑、以Ce_0.8Gd_0.2O_2-δ(GDC)为电解质、以La_0.8Sr_0.2Co_0.8Fe_0.2O_3-δ(LSCF)-GDC为复合阴极的单电池。利用XRD和SEM等方法对阳极材料EDC进行了晶相结构、微观形貌和化学相容性等分析。在400~700 ℃范围内,以加湿天然气(3% H₂O)为燃料气,氧气为氧化气测试了电池的电化学性能。结果表明：EDC阳极材料具有良好的孔道结构;11种不同阳极组成的单电池中50%(质量分数)NiO-50%(质量分数)Ce_0.85Er_0.15O_y(E15C85)阳极支撑的单电池具有最佳的电化学性能,在650 ℃时其最大电流密度为117.84 mA·cm^-2和最大比功率为24.37 mW·cm^-2。     

Nanostructure and conductivity study of yttria doped zirconia films deposited on samaria doped ceria

Yttrium doped zirconia (YSZ) film was deposited on poly-crystalline 10 at.% samaria doped ceria (SDC) and YSZ plate (doped with 8 at.% yttria) by electron beam evaporation deposition. For electrolyte application in solid oxide fuel cells, YSZ can be used with SDC and act as an electron barrier. The conductivity of YSZ and SDC was measured after sintering at 1000 °C. Results indicated that YSZ film became columnar structure, and a new layer formed between the YSZ film and SDC, due to the inter-diffusion between zirconium ions and cerium ions.     

银基陶瓷复合电极的电性能及其在固体氧化物燃料电池中的应用

银基陶瓷复合电极可望在中低温固体氧化物燃料电池(SOFCs)、含碳燃料SOFCs和固体氧化物电解池(SOECs)中得到广泛应用。为优选出银基陶瓷复合电极的成分,本研究采用YSZ(钇稳定化氧化锆)电解质,先将Ag-YSZ和Ag-GDC(掺钆氧化铈)材料制备成对称电极,测试其在空气下的阻抗谱,由此判断其作为阴极的性能;发现在相同的Ag含量时, Ag-YSZ的阴极极化电阻普遍低于Ag-GDC;当Ag的质量分数为65%时, Ag-YSZ的极化电阻最低,而对于Ag-GDC, Ag的质量分数是70%。然后采用空气中极化电阻最低的Ag-YSZ和Ag-GDC作为电极制备了SOFC单电池,并采用加湿氢气燃料对电池的电化学性能进行了测试。根据电池的阻抗谱数据,将极化阻抗的数值减去上述阴极阻抗的数值可得到阳极阻抗值,其结果和电池的输出特性均表明, Ag-GDC作为阳极的性能优于Ag-YSZ,即在本实验条件下, Ag-YSZ更适合用作阴极,而Ag-GDC更适合用作阳极。本研究不仅提供了关于银基复合电极材料的有用数据,还提供了一种测试SOFC阳极极化电阻的方法。     

Economizing on Precious Metals in Three‐Way Catalysts: Thermally Stable and Highly Active Single‐Atom Rhodium on Ceria for NO Abatement under Dry and Industrially Relevant Conditions**

We show for the first time that atomically dispersed Rh cations on ceria, prepared by a high‐temperature atom‐trapping synthesis, are the active species for the (CO+NO) reaction. This provides a direct link with the organometallic homogeneous Rh^I complexes capable of catalyzing the dry (CO+NO) reaction. The thermally stable Rh cations in 0.1 wt % Rh₁/CeO₂ achieve full NO conversion with a turn‐over‐frequency (TOF) of around 330 h^?1 per Rh atom at 120 °C. Under dry conditions, the main product above 100 °C is N₂ with N₂O being the minor product. The presence of water promotes low‐temperature activity of 0.1 wt % Rh₁/CeO₂. In the wet stream, ammonia and nitrogen are the main products above 120 °C. The uniformity of Rh ions on the support, allows us to detect the intermediates of (CO+NO) reaction via IR measurements on Rh cations on zeolite and ceria. We also show that NH₃ formation correlates with the water gas shift (WGS) activity of the material and detect the formation of Rh hydride species spectroscopically.     

On the Flocculation and Agglomeration of Ceria Dispersion

The ceria dispersions displayed a maximum in the yield stress at the isoelectric point (pI) at pH ～ 7. At pH below pI, the flocculated dispersions at solids concentration of 30 wt% and above produced a smooth and homogeneous appearance. However, at pH above pI, phase separation was observed to occur quite quickly forming a clear layer of liquid supernatant. Upon examination, relatively large discrete aggregates had formed. This behavior can be explained by the surface chemical model proposed by Nabavi et al.^{[ 1} Nabavi , M. , Spalla , O. , and Cabane , B. ( 1993 ) J. Colloid Interface Sci. , 160 : 459 – 471 . [Google Scholar] ^] According to Nabavi et al., nitrate anion, normally an indifferent electrolyte, is both adsorbed and bounded covalently to the surface of the ceria particles at pH below pI. A steric layer is formed preventing particle agglomeration. Such agglomeration was also prevented at high pH with the adsorption of pyrophosphate additive added at 1dwb% concentration. The model proposed by Nabavi et al also explained the agglomeration of ceria particles at pH > pI. Both the covalently bounded and adsorbed nitrates were displaced by the hydroxyl group forming this surface ?OH group that on the interacting particles condenses to form ?Ce?O?Ce? bridging bond and caused particle agglomeration. The yield stress-DLVO force model was obeyed by the ceria dispersion at pH below pI. A critical zeta potential of 56 mV was obtained and this gives an estimate value for its Hamaker constant in water of 82 zJ.     

Investigation of the Pore Texture of SnO2-CeO2 Composite Oxides

Gas adsorption techniques have been used to study the pore texture changes occurring in composite SnO₂-CeO₂ materials of varying Sn: Ce atom ratios on calcination at temperatures up to 1273K. The data show that the uncalcined materials are largely microporous in nature, but changes in specific surface area, pore sizes and pore volume occur at an early stage in the calcination process with the formation of mesopores. However, significant changes occur at calcination temperatures>673 K at which point the mesopores are substantially reduced, and at 873 K and above the mean pore size increases greatly finally giving non-porous solids after calcination at 1273 K.     

Preparation of CeO2-ZrO2 Mixed Oxide Powders by the Coprecipitation Method for the Purification Catalysts of Automotive Emission

Influence of CeO₂ content on the specific surface area (SA), oxygen storage capacity (OSC) and crystalline structure of the powders in the CeO₂-ZrO₂ system were investigated. The change of SA value by heat-treatment is almost proportional to that of OSC. The lattice parameters of the powders had a linear relationship with the OSC value. In the CeO₂-ZrO₂ system, powders with 20 mol% CeO₂ was found to show the highest OSC value and the highest durability of SA value after calcined at high temperatures.     

Phase Analysis and Oxygen Storage Capacity of Ceria-Lanthana-Based TWC Promoters Prepared by Sol-Gel Routes

Ceria-lanthana-based promoters of three-way catalysts are synthesized by two different sol-gel routes, involving nitrate precursors. The oxygen uptake ability of these compounds is measured by O₂ chemisorption. The specific surface area is determined by N₂ adsorption (BET). X-ray diffraction data are analyzed by Rietveld refinement, demonstrating that lanthanum forms solid solution with CeO₂; its total amount in ceria depends on the competitive formation of La-Al mixed oxides and on the synthetic method. The O₂ uptake ability is essentially determined by the La content in the ceria-lanthana solid solution, while it is independent on the surface area and on the CeO₂ particle size. The O₂ uptake ability increases with the La:Ce relative amount in the ceria-lanthana solid solution, but decreases beyond a La:Ce molar ratio greater than ?0.18. This behavior is ascribed to the stable association of vacancy-vacancy or vacancy dopant cation.