Influences of Platinum Precursors and Solution Acidities on REO-Based Catalysts Performances

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.

Effect of doping elements on catalytic performance of CeO_2-ZrO_2 solid solutions

CeZr, CeYZr, LaCeZr, LaCePrZr, LaCePrYZr, and LaCePr solid solutions were prepared via the coprecipitation method, and characterized by means of X-Ray Diffraction （XRD） and Brunauer-Emmett-Teller （BET） techniques. The oxygen storage capacity （OSC） of the solid solutions was evaluated by the pulse technique and the catalytic activity was assessed using a 4-channel catalysis device. It was seen that the solid solutions presented cubic structure. The specific surface area and thermal stability could be enhanced by doping Y into the solid solutions. Doping a small amount of La had a positive effect on the thermal durability while doping a large amount of La decreased the specific surface area and the thermal stability. LaCePrZr and LaCePrYZr solid solutions synthesized using Baotou rare earth mineral residue enriched with LaCePr after Nd extraction presented a certain higher value in specific surface area and thermal stability, thereby enabling to be used as economic catalysts for automobile exhaust purification. Coating Al2O3 or SiO2 layer on the surface of ceria-zirconia solid solutions increased the specific surface area and thermal resistance.

Surface and Texture Properties of Tb-Doped Ceria-Zirconia Solid Solution Prepared by Sol-Gel Method

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.

铈锆氧化物固溶体对全钯三效催化剂性能的影响

采用共沉淀技术制备出了Ce0 .6 Zr0 .4 O2 固溶体 ,并对其进行了比表面积测试和XRD表征。将其用于全钯三效催化剂的制备 ,考察了Ce0 .6 Zr0 .4 O2 对三效催化剂性能的影响。结果表明 ,Ce0 .6 Zr0 .4 O2 具有和CeO2 相似的立方结构 ,其比表面积随着温度的升高下降速度比CeO2 慢。和含CeO2 的三效催化剂相比 ,含Ce0 .6 Zr0 .4O2 的三效催化剂经高温老化后 ,HC、CO。

A rationale for the development of thermally stable nanostructured CeO_2-ZrO_2-containing mixed oxides

CeO2-ZeO2 solid solutions are extensively used as oxygen storage promoters in the current automotive three-way catalysts. High thermal stability of the textural properties is one of the most important requirements for practical application since temperatures up to 1273 K are easily experienced by these materials under real working conditions. In the present paper, we investigated how hydrothermal treatments applied to cakes of doped and undoped ZrO2-rich CeO2-ZrO2 precursors might improve the thermal stability of the final CeO2-ZrO2 solid solution. A rationale was developed that allowed to correlate the morphology of the hydrothermaUy treated cake with the thermal stability at 1273 K of the final product, which did not depend on the composition of the mixed oxides.

贵金属/铈锆铽固溶体催化剂的制备与台架性能评价

用Ce0.6Zr0.3Tb0.1O2作为储氧材料,分别制备了实尺寸的全钯三效催化剂和双层钯、铂、铑三效催化剂。为作对比,同时制备了含商用铈锆固溶体的双层钯、铂、铑三效催化剂。在发动机台架上对所制备的催化剂进行了活性评价。3种催化剂具有较高的三效催化活性,在交叉点附近对CO和NOx的转化率接近100%,对THC的转化率接近90%。双层催化剂和单层全钯催化剂相比,不仅在富燃区具有较高的NOx转化率,而且具有较低的起燃温度。含Ce0.6Zr0.3Tb0.1O2固溶体的双层催化剂的性能优于含商用铈锆固溶体的催化剂。

三效催化剂用储氧材料的研究进展

论述了国内外储氧材料的研究进展,简述了不同种类的储氧材料。对固溶体储氧材料CeO2的改性研究表明,过渡金属元素或稀土金属元素被嵌入CeO2晶格形成固溶体,可极大地改善CeO2基储氧材料的储氧性能和热稳定性能,促进CeO2基储氧材料广泛的实际应用。

Ni-La/Ce_xZr_(1-x)O_2催化剂制备及其甲烷部分氧化/CH_4-CO_2重整耦合制合成气反应性能

通过共沉淀法制备铈锆固溶体作为载体,采用等体积、分步浸渍的方法制备了一系列10%Ni-3%La/Ce x Zr1-x O2(x=0、0.16、0.5、0.75、1)催化剂,并将其应用到甲烷部分氧化和甲烷二氧化碳重整耦合制合成气的反应中.对不同Ce/Zr比的催化剂性能展开研究,采用BET、XRD、H2-TPR、SEM、TG-DSC手段对载体及催化剂进行了表征.结果表明,铈锆固溶体的形成不仅提高了催化剂表面活性组分的分散度,使催化剂表面NiO晶粒尺寸从26.5 nm减到13.7 nm;而且能够加强活性组分与载体之间的相互作用,提高催化剂的热稳定性能;随着Ce/Zr比的增加,催化剂的转化率、选择性及稳定性随之增高,其顺序为:Ni-La/Ce0.75Zr0.25O2>Ni-La/Ce0.5Zr0.5O2>NiLa/Ce0.16Zr0.84O2.

Preparation of Ce_(0.65)Zr_(0.35)O_2 by co-precipitation: The role of hydrogen peroxide

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.

水汽-CO_2环境下Pt/CeZrO_2催化剂的CO氧化性能研究

采用浸渍法制备了Pt/Ce0.6Zr0.4O_2粉末催化剂,涂覆到蜂窝陶瓷载体表面得到整体式催化剂。考察了Pt含量及焙烧温度对催化剂在水汽-CO_2环境下催化CO氧化性能的影响,并用XRD,TEM和H2-TPR等手段对载体和催化剂进行了表征。结果表明,在空速50000 h-1的反应条件下,当焙烧温度为300℃时,3.0Pt/Ce0.6Zr0.4O_2整体式催化剂的CO氧化活性最高,反应温度200℃时,CO转化率为87%,具有较高的水汽-CO_2环境下的CO氧化活性。通过对2.0Pt/Ce0.6Zr0.4O_2催化剂在无水汽,无CO_2,无水汽-CO_2及水汽-CO_2环境下的对比实验,发现水汽和CO_2对催化剂的活性有明显的抑制作用,水汽的影响比CO_2的影响要更大一些。这说明水汽、CO_2和CO对催化剂存在竞争吸附。结合催化剂的H2-TPR表征结果,发现催化剂的还原能力越高,相对应的CO氧化活性也越高。添加适量的Pt有利于提高催化剂的还原能力,从而提高其活性,但是过量的Pt会使催化剂活性下降。