Oxygen Storage Capacity of Pt-, Pd-, Rh/CeO_2-Based Oxide Catalyst

CZO （CeO2-ZrO2） and CZYO （CeO2-ZrO2-Y2O3） series of mixed oxides were prepared by coprecipitaion, and a part of these oxides were loaded with precious metals （PM）. XRD, BET, and oxygen storage capacity （OSC） investigations were performed on samples aged at 750, 900, and 1050 ℃. It was observed that BET surface area and OSC showed a marked decrease in CeO2 aged at high temperature, and the erystallite size showed an obvious increase. The CZO samples consist of cubic- and tetragonal crvstal phases, and their crystallite size increase rapidly when aged at high temperature. The CZYO samples consist of single crystal phase when the content of Y exceeds 0.15 mol, and their erystallite size increases slowly during high-temperature aging. It is concluded that additive Y can stabilize the performance of CZYO oxides. In the aged CZO and CZYO mixed-oxide systems, addition of a small amount of precious metals （Pt, Pd, Rh） increased the rate of reduction and led to an obvious improvement in OSC. OSC of CZO and CZYO with precious metals are related to their composition and the type of precious metal.

Dynamic Oxygen Storage Capacity Measurements on Ceria-Based Material

Dynamic oxygen storage and release capability （OSC） measurement apparatus was designed to evaluate the OSC performance of ceria-based oxygen storage material. The optimum measurement condition was at a frequency of 0.1 Hz with the inlet gas-flow sequence CO （5S）→O2（5S）→CO→O2 and a flow rate of 300 ml·min^-1. Under this condition, similar regular square wave in the inlet and outlet of the reactor was obtained to guarantee the reliability of the dynamic OSC results. The dynamic OSC performance of the CeO2 and Ce0.67Zr0.33O2 mixed oxide prepared using the citric sol-gel method was studied at the optimum measurement condition with focus on both quantitative and qualitative analyses, The results reveal distinctly that Ce0.67Zr0.33O2 had better dynamic OSC performance because of its higher oxygen migration rate than CeO2. Under dynamic conditions, two CO2 production peaks occurred corresponding to the CO pulse and the O2 pulse, respectively, during the entire cycle. The intensity and ratio between the two CO2 productions were highly influenced by temperature and frequency indicating complex surface phenomena during the oxygen storage/release process, As a result, this set-up can be applied to the evaluation of ceria-based material on the OSC performance.

Oxygen Storage Capacity and Adsorptive Property of Praseodymium Oxides

Oxygen storage and adsorptive properties of praseodymium oxides were investigated by pulse experiments and temperature - programmed desportion/reduction (TPD/TPR) experiments. Pr2O3 possesses the similar oxygen storage properties to CeO2, and its dynamic oxygen storage capacity is 14.9 mumol.g(-1). The studies on TPD Of O-2, H2O and CO and TPR show that Pr2O3 provides more active surface oxygen species and at a lower temperature than CeO2. It is suggested that Pr2O3 can be a well candidate as an oxygen storage component in automobile three-way catalyst.

Novel Oxygen Storage Components Promoted Palladium Catalysts for Emission Control in Natural Gas Powered Engines

A three-way catalyst comprised novel oxygen storage components for emission control in natural gas powered engines was prepared. The addition of novel oxygen storage components to the Pd/γ-Al2O3 catalysts resulted in improved activities of the fresh and aged catalyst by lowering the light-off temperature for methane in natural gas engines exhaust.

Role of Surface Adsorption in Fast Oxygen Storage/Release of CeO_2-ZrO_2 Mixed Oxides

Four kinds of CeO2-ZrO2 mixed oxides, i.e., a physical mixture of ceria and zirconia （CZP）, zirconia-coated ceria （ZCC）, ceria-coated zirconia （CCZ） and a chemical mixture of celia and zirconia （CZC）, were prepared. The oxygen storage capacity （OSC） measurements at 500℃ were performed under transient and stationary reaction conditions. All the curves of CO2 evolution during CO-O2 cycles presented a bimodal shape. The fast peak was primarily the result of the reaction of CO with the oxygen from the oxides, which was mainly determined by the nature of the material The sec- ond peak was mostly related to the CO2 adsorption behavior and was highly influenced by the surface area and the number of surface active sites. As a result, OSC activity of the samples followed in the order of CZC 〉 CCZ 〉 ZCC=CZP.

Structure and oxygen storage capacity of Pd/Pr/CeO_2-ZrO_2 catalyst:effects of impregnated praseodymia

Praseodymium （Pr） was impregnated to CeO2-ZrO2 solid solution by an impregnation method. The as-obtained Pr modi- fied CeO2-ZrO2 was impregnated with 1 wt.% Pd to prepare the catalysts. The structure and reducibility of the fresh and hydrother- really aged catalysts were characterized by X-ray diffraction （XRD）, Raman, X-ray photoelectron spectroscopy （XPS）, CO chemi- sorption and H2 temperature-programmed reduction （H2-TPR）. The oxygen storage capacity （OSC） was evaluated with CO serving as probe gas. Effects of impregnated Pr on the structure and oxygen storage capacity of catalysts were investigated. The results showed that the aged Pr-impregnated samples had much higher OSC and better reducibility than the unmodified ones. The scheme of structural evolutions of the catalysts with and without Pr was also established. Partial of the impregnated Pr diffused into the bulk of CeO2-ZrO2 during ageing, which inhibited the sintering, and increased the amount of oxygen vacancies in CeO2-ZrO2 support. Furthermore, those impregnated Pr species which covered on the surface of the support obstructed the strong metal-support interaction between Pd and Ce so as to reduce the encapsulation of Pd as well as the back spill-over of the oxygen during the catalytic process.

Effect of grain size on thermal stability and oxygen storage capacity of Ce_(0.17)Zr_(0.73)La_(0.02)Nd_(0.04)Y_(0.04)O_2 solid solutions

Nanostructured CeO_2-ZrO_2 materials are an irreplaceable constituent in catalytic systems for automobile exhaust purification due to their unique oxygen storage capacity(OSC). However, traditional CeO_2-ZrO_2 materials are easy to sinter at high temperature, which causes a sharp decrease of OSC. In this paper,La^(3+) , Nd^(3+) and Y^(3+) are chosen as dopants for CeO_2-ZrO_2 to improve anti-sintering and OSC properties.The Ce_(0.17) Zr_(0.73) La_(0.02) Nd_(0.04) Y_(0.04) O_2 powders(CZLNY) were prepared by co-precipitation method. The effects of grain sizes with different mixed chlorinated solution concentrations on performances were investigated. X-ray diffraction(XRD) and transmission electron micrograph(TEM) were performed to calculate the grain sizes of CZLNY. The specific surfaces, OSC and redox properties were investigated by N_2 adsorption/desorption and temperature programmed reduction(H2-TPR). The results show that introducing La^(3+) , Nd^(3+) and Y^(3+) into CeO_2-ZrO_2 lattice can improve the stability of phase structure and anti-sintering ability. Moreover, low concentration of mixed chlorinated solution remarkably improves structural and textural properties of CZLNY. Relatively large fresh grain exhibits superior thermal stability and OSC under the condition of being calcined at 800℃ for 3 h. The specific surface and OSC are42.37 m^2/g and 333.13 mmol/g after calcining at 1000℃ for 10 h, respectively. This is owing to the low sintered driving force of large grain and long-range migration energy of large pores during the sintering process, which are beneficial to the stability of structure in CZLNY materials.

Effect of cobalt doping on ceria-zirconia mixed oxide: Structural characteristics, oxygen storage/release capacity and three-way catalytic performance

The effect of Co doping on ceria-zirconia mixed oxides was investigated for Co0.1Ce0.6Zr0.3Ox sample prepared by sol-gel method. The Pd-only three-way catalyst （TWC） was obtained by incipient wetness impregnation with 0.5 wt.% Pd loading. The structural and oxygen handling properties were analyzed by X-ray diffraction （XRD）, H2-temperature programmed reduction （H2-TPR） and the dynamic oxygen storage capacity （DOSC）. The introduction of Co into ceria-zirconia lattice strongly modified the mobility of oxygen and enhanced the DOSC performance. Pd-only TWC based on the Co0.1Ce0.6Zr0.3Ox support exhibited superior activity for water-gas shift and steam reforming and ampli- fied amplitude of stoichiometric window.

共沉淀法制备高热稳定性铈锆复合氧化物的工艺优化及其储放氧性能

铈锆复合氧化物是汽车尾气净化三效催化剂的关键组分之一。日益严格的排放法规对铈锆复合氧化物的热稳定性提出了更高的要求。通过共沉淀法合成高热稳定性CeO_(2)-ZrO_(2)复合氧化物,考察掺杂改性元素、前驱体盐种类、洗涤方法以及陈化条件对样品比表面积和热稳定性的影响。结果表明,采用La-Y-Nd共掺杂作为改性组分,以含Ce^(4+)的Ce(NH_(4))_(2)(NO_(3))_(6)作为铈盐前驱体,采用无水乙醇洗涤,在乙醇环境陈化12 h得到的CeO_(2)/ZrO_(2)/La_(2)O_(3)/Y_(2)O_(3)/Nd_(2)O_(3)(CZLYN)样品具有最优的比表面积与热稳定性,经马弗炉1050℃老化12 h后仍能维持38 m^(2)·g^(-1)的比表面积。将优化工艺下制备的CZLYN样品与某进口商用铈锆粉进行表征对比,发现其与商用铈锆粉具有相似的物相结构、晶粒尺寸、孔径分布和表面微观形貌,且新鲜样比表面积提高约60%;经过1050℃马弗炉热老化后,优化工艺CZLYN样品比表面积较商用铈锆粉提高约20%;水热老化后,优化工艺CZLYN样品比表面积仍略高于进口商用铈锆粉,动态储放氧性能高约30%,表明其具有更为优异的热稳定性。

Fabrication and characterization of Ce_(0.7)Zr_( 0.3)O_2 nanorods having high specific surface area and large oxygen storage capacity

Nanorod-like Ce0.7Zr0.3O2 solid solutions were synthesized by a sodium dodecyl sulfate-assisted precipitation method. The samples were characterized by means of scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and specific surface area measurement. Typical Ce0.7Zr0.3O2 nanorods were 40 nm in average diameter and 450 nm in length, with specific surface area and oxygen storage capacity of 194 m2/g and 374 μmol/g, respectively.

Structure and oxygen storage capacity of Pr-doped Ce_(0.26)Zr_(0.74)O_2 mixed oxides

Binary Ce-Zr（CZ）,Pr-Zr（PZ） and ternary Ce-Zr-Pr（CZP） mixed oxides were prepared by an ammonia-aided co-precipitation method,and were aged in a steam/air flow at 1050 °C.X-ray diffraction（XRD）,Raman spectra,X-photon spectra（XPS） and CO temperature programmed reduction（TPR） were carried out to characterize the micro-structure and reducibility of catalysts.The oxygen storage capacity（OSC） was evaluated with CO serving as probe gas.The results showed that a pseudo cubic structure was formed for the Zr-rich ceria-zirconia mixed oxides with Pr doping.The insertion of Pr prevented the phase segregation of the mixed oxides during the hydrothermal ageing.The Pr doped samples showed better redox performances in comparison with CZ,and the sample doped with 5 wt.% Pr showed the most remarkably promoted dynamic oxygen storage capacity.This phenomenon was closely related to both the reducibility and oxygen mobility of the mixed oxides.The introduction of praseodymium into ceria-zirconia could accelerate the oxygen migration by increasing the amount of oxygen vacancies,although it was difficult for Pr3＋ ions themselves to participate in the oxygen exchange process.

Synthesis and characterization of Nd^(3+)-doped Ce_(0.6)Zr_(0.4)O_(2) and its doping significance on oxygen storage capacity

Cerium and cerium-based oxides are found to be an important element in three-way catalytic converter(TWC).The effective utilization of TWC is found to be reduced due to thermal loading which results in structural deformation of ceria,Doping Zr^(4+)into the rare earth element can increase the oxygen storage capacity and thermal stability.Hence,an attempt was made to study the oxygen storage capacity and thermal stability of ceria by doping Zr^(4+)and Nd^(3+).Cerium-based nanocrystallite in the composition of Ce_(0.6)Zr_(0.4-x)Nd_(1.3)xO_(2)(0≤x≤0.4)was prepared by sol-gel synthesize technique with citric acid as a gel-forming agent.X-ray diffraction(XRD)result shows that doping Nd^(3+)into ceria lattice forms homogenous solid solution of cubic fluorite structure up to 25%of substitute only.Doping higher amount of Nd^(3+)into ceria lattice leads to the formation of Nd_(2)O_(3).Raman spectrum study confirms that oxygen storage capacity band is present in Ce_(0.6)Zr_(0.4)O2 and Ce_(0.6)Zr_(0.3)Nd_(0.13)O_(2).The oxygen storage capacity was calculated through weight loss of the sample during the second heating cycle with cyclic heating from30 to 800℃in thermogravimetric analysis(TGA).The TGA study reveals that the oxygen storage capacity of Ce_(0.6)Zr_(0.4)O2 decreases after the substitution of Nd^(3+),which is due to the larger ionic radius of Nd^(3+)compared with that of Zr4+and CeO2.

新一代三效催化剂的关键材料─Ce_xZr_(1-x)O_2固溶体研究进展

汽车尾气排放法规的日趋严格迫切要求开发高性能的三效催化剂。传统三效催化剂中的CeO2 高温下易发生烧结而降低或失去储氧能力。而加入锆所形成的CexZr1 -xO2 固溶体具有良好的抗高温老化性能、低温还原性能和较高的储氧能力 ,可以作为新一代三效催化剂的关键材料。

晶格氧部分氧化甲烷制合成气

用储氧材料中的晶格氧代替分子氧部分氧化甲烷制合成气,并以空气、H2O或CO2为氧源对失去晶格氧的储氧材料进行氧化再生,是一种通过气固反应制取合成气的新工艺,具有较高经济效益和环境效益。本文综述了该技术在储氧材料和反应体系等方面的研究进展,并从合成气和金属联产工艺以及熔融盐储能的研究思路中得出了一些启示,对该技术今后的研究重点和应用领域进行了展望。

铈锆摩尔比对Ce_(0.3+x)Zr_(0.6-x)Y_(0.1)O_(1.95)系列储氧材料性能的影响

A series of materials Ce0.3+xZr0.6-xY0.1O1.95 were prepared by co-precipitation routine and the property of these materials was studied by means of oxygen storage capacity, temperature programming reduction, X-ray diffraction, transmission electronic microscope, and X-ray photoelectron spectroscopy. The results indicate that the materials with a low Ce/Zr molar ratio possess higher cerium atom utilization ratio, reducibility and thermal stability than the materials with a high Ce/Zr ratio, and Ce0.35Zr0.55Y0.1O1.95 possesses the best properties.

高性能Ce_(0.35)Zr_(0.55)Y_(0.1)O_(1.95)稀土储氧材料的研究

The oxygen storage material (OSM) Ce0.35Zr0.55Y0.1O1.95 was prepared by co-precipitation routine and studied by means of TEM, XRD, XPS, BET, H2-TPR and oxygen storage capacity (OSC) measurements. The results indicated that this material possessed plenty of Ce3+ and lattice oxygen vacancy (percentage of Ce3+ was 59.6%) and high cerium atom utilization ratio (80.04%). The porous material was with an average BET surface area of 97 m2·g-1 and pore volume of 0.26 mL·g-1. After aged at 1 000 ℃ in air for 5 h, the sample still possessed plenty of Ce3+ and lattice oxygen vacancy (percentage of Ce3+ was 57.1%), and showed high cerium atom utilization ratio (78.25%), and high thermal stability.

不同保存时间的库存红细胞携氧能力变化研究

目的建立红细胞携氧能力相关评价指标与库存时间的数学模型,为红细胞定量输注提供实验依据。方法随机选取6名合格献血者,采集红细胞1 U/人(全血200 mL=1 U)制备成悬浮红细胞,置于专用储血冰箱,分别在库存0、7、14、21、28和35 d留取血样,测定有效携氧量(Q值)、氧亲和力(P50)、2,3-DPG、Na+-K+-ATP酶,综合评价红细胞携氧能力;应用统计学软件对数据进行曲线拟合分析,获得计算各携氧能力指标与库存时间的数学模型。结果在保存期内的红细胞Q值随库存时间的增加而逐渐下降:库存14 d前下降较快,至14 d下降了32%,之后下降变缓,到保存末期仅为库存0 d红细胞的49%;P50随库存时间的增加而逐渐下降:库存14 d前下降较快,至14 d下降了19%,之后下降不明显,到保存末期为库存0 d红细胞的71%;2,3-DPG随库存时间的增加而逐渐下降:库存21 d前缓慢下降,之后出现急速下降,到储存期末仅为库存0 d红细胞的41%;Na+-K+-ATP酶随库存时间的增加而逐渐下降:库存前7 d下降最为剧烈,下降54%,之后下降速度变缓,到储存期末仅为库存0 d红细胞的15%;对数据曲线的拟合分析显示:以Q值为因变量Y,库存时间为自变量X,得出回归方程为Y=4.367-0.066X;以P50为因变量Y,库存时间为自变量X,得出Y=28.346-0.234X;以2,3-DPG为因变量Y,库存时间为自变量X,得出Y=1.875-0.030X;以Na+-K+-ATP酶为因变量Y,库存时间为自变量X,得出为Y=4.534-0.127X。Q值和P50完全线性相关(r=0.999 43),与库存时间、2,3-DPG、Na+-K+-ATP酶存在回归关系,其多元线性模型为Q=5.457-0.925×2,3-DPG+0.142×Na+-K+-ATP酶-0.076×T(库存天数)。结论 Q值测定水平可以作为库存红细胞携氧能力评价的重要指标,并可根据其变化计算不同库存时间红细胞的携氧能力。红细胞随库存时间的延长其携氧能力不断下降,库存前2周其携氧能力下降的尤为明显,贮存35 d的红细胞携氧能力仅为0 d的50%。

高热稳定性、高比表面积低铈型铈锆钇储氧材料的制备及其性能研究

采用氨水-碳酸铵混合沉淀剂制备了低铈型铈锆钇三组分储氧材料.采用X射线衍射、BET、氧脉冲吸附和H2程序升温还原(H2-TPR)等技术对材料的晶体结构、比表面积、孔结构、储氧性能和还原性能进行了研究.结果表明,该材料经873 K焙烧4 h后比表面积达到116.8 m2/g,孔容达到0.30 cm3/g,经1 273 K老化10 h后,比表面积和孔容仍然保持在68.1 m2/g和0.22 cm3/g.由XRD结果可知,材料的物相组成为四方相的Zr0.84Ce0.16O2,在热处理过程中物相结构稳定.氧脉冲吸附和程序升温还原的结果表明,材料储氧性能保持较好.

掺杂钇铋Ce-Zr-Al储氧材料的制备及性能研究

采用共沉淀法制备了掺杂Y3+、Bi3+的CeO2-ZrO2-Al2O3(CZA)储氧材料,并通过XRD、低温N2吸附-脱附、氧脉冲吸附(OSC)及H2-TPR等手段进行了表征.XRD结果表明,600℃和1000℃焙烧后,Y3+、Bi3+的加入没有改变物相结构,所有样品均形成单一立方相萤石结构固溶体.低温N2吸附结果表明,Y3+掺杂的Ce0.6Zr0.3Y0.1O1.95-Al2O3(CZYA)材料,其织构性能及热稳定性都有很大的改善,1000℃老化5h后,比表面积和孔容可分别达80.75m2/g和0.22mL/g.OSC和H2-TPR结果表明,同时掺杂Y3+、Bi3+的Ce0.6Zr0.2Y0.1Bi0.1O1.9-Al2O3(CZYBA)材料,其储氧性能明显增强,经600和1000℃焙烧后分别达到461和242μmol/g;同时掺杂Y3+、Bi3+增强了CZA材料的还原性能,1000℃老化5h后还原峰温度从546℃降低到429℃.

不同铈添加量对CeO_2-ZrO_2-Al_2O_3材料性能的影响

采用共沉淀法制备了一系列不同铈添加量的CeO2-ZrO2-Al2O3(CZA)储氧材料,并通过XRD、低温N2吸附-脱附、氧脉冲吸附(OSC)和H2-TPR等手段进行了表征。XRD结果表明,在1 000和1 100℃高温焙烧后,当CeO2添加量为8%时样品具有最好的结构稳定性能。N2吸附-脱附结果表明,CeO2添加量为8%时样品具有最好的织构性能,1 000℃时,比表面积和孔容分别为:136.6 m2.g-1和0.38 mL.g-1;1 100℃时,比表面积和孔容分别为:83.7 m2.g-1和0.23 mL.g-1。OSC结果显示,CeO2添加量为8%时样品具有最大的储氧量,1 000℃和1 100℃分别为70μmol.g-1和31μmol.g-1。H2-TPR结果表明,CeO2添加量为8%时样品具有最佳的还原性能。