掺杂不同量Nd2O3对CeO2-ZrO2-Al2O3材料性能的影响

采用共沉淀法制备了一系列Nd2O3含量为0～13wt%的CeO2-ZrO2-A12O3(CZA)复合氧化物,并通过X射线衍射(XRD)、低温N2吸附–脱附、氧脉冲吸附(OSC)、H2–程序升温还原(H2-TPR)及扫描电子显微镜(SEM)等方法对所制备的材料进行了表征.研究结果表明,Nd2O3在CZA固溶体中的溶解限约为10wt%,过量Nd的添加会出现分相形成Nd0.5Ce0.5O1.75氧化物.掺杂适量Nd能有效抑制氧化物晶粒的长大,提高材料的热稳定性和氧化还原性能.Nd2O3的掺杂量为10wt%时,样品的织构稳定性最好,1000℃老化5 h后,比表面积和孔容分别达97.14 m2/g和0.44 mL/g.Nd2O3的掺杂量为7wt%时,样品有高的储氧量,经600℃和1000℃焙烧后储氧量分别为938.01μmol/g和821.72μmol/g;体相氧的移动能力最强,还原性能最佳,老化后还原峰温由465℃升高到483℃.SEM结果表明,所制备的材料均为球形颗粒,Nd2O3的添加可以有效阻止高温焙烧过程中粒子的团聚.     

陈化体系中醇对Ce0.65Zr0.35O2及其负载的单Pd催化剂性能的影响

采用共沉淀法制备了Ce_0.65Zr_0.35O₂(CZ)储氧材料, 分别以乙醇-水、丙醇-水、乙二醇-水、丙三醇-水体系对沉淀物进行陈化, 研究了醇的种类对CZ及其负载的单Pd催化剂性能的影响。对CZ进行了扫描电镜(SEM), N₂-吸脱附分析, 对Pd/CZ进行了粉末X射线衍射(XRD)、X射线光电子能谱(XPS)、储氧量 (OSC)和程序升温还原( H₂-TPR)的表征, 并考察了三效催化性能。结果表明, 醇的种类对CZ及Pd/CZ的性能有显著影响。在乙醇-水和丙醇-水陈化体系中制备的CZ分散性高, 颗粒堆积松散, 比表面积和孔径大, 孔容高, 且具有优异的热稳定性, 其中丙醇-水陈化体系中制备的CZ老化后比表面积和孔容分别可达28 m²/g和0.1 mL/g, 具有最高的热稳定性, 其负载的单Pd催化剂在老化后对C₃H₈、CO和NO转化显著优于乙二醇-水和丙三醇-水陈化体系中制备的CZ所制备的催化剂。     

Synthesis of neodymium modified CeO2-ZrO2-Al2O3 support materials and their application in Pd-only three-way catalysts

Ce-Zr-Al-Nd2O3 (CZAN) support materials were prepared by co-precipitation and impregnation methods, respectively. They were characterized by X-ray diffraction (XRD), low temperature nitrogen adsorption-desorption, oxygen pulsing technique, H2-temperature pro-grammed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS). The Pd-only three-way catalysts (Pd-TWC) supported on these materials were prepared by incipient wetness method and studied by activity tests. The results demonstrated that the CZAN supports obtained by the two methods showed better structural, textural and redox properties than the CZA without Nd2O3, and the addition of Nd2O3 improved the catalytic activity of TWC. Especially, the CZAN-i support prepared by impregnation method had better thermal stability and redox prop-erty. Meanwhile, the Pd/CZAN-i catalyst exhibited the best catalytic performance. XPS measurements indicated that the Nd-modified sam-ples possessed more Ce3+ and oxygen vacancies on the surface of samples, which led to a better redox property. The excellent redox property of support materials helped to improve the catalytic activity of TWC.     

性能优异的SrO改性Pd-Rh双金属催化剂的制备

在浸渍到Al₂O₃载体材料上之前,通过将Sr的前驱体引入到贵金属Pd和Rh的混合盐溶液中,即采用共浸渍法制备了一系列SrO改性的Pd-Rh/Al₂O₃催化剂。结果表明,由于SrO的扩散障碍效应,适量SrO（1%~2%,质量分数）的引入有利于促进Pd,Rh的分散,并且能提高催化剂的水热稳定性。水热老化之后,催化剂能保持更高的Pd,Rh分散度,并且Pd,Rh能稳定在活性更好的氧化态。因此,适量SrO改性的Pd-Rh/Al₂O₃催化剂具有更好的还原性能和三效催化活性。然而,当向催化剂中引入过量的SrO,由于SrO占据了过量的Al₂O₃的表面,而且老化后会出现新的物相SrAl₂O₄,反而会对催化剂的性能产生不利的影响。总的来说,2% SrO改性的催化剂具有最优异的三效催化活性,水热老化之后,相比于空白的Pd-Rh/Al₂O₃催化剂,2%SrO改性的催化剂使CO,HC和NO的起燃温度分别降低了23,15和27 ℃。     

用于高性能单Pd三效催化剂的复合组分CexZr1-xO2材料的制备

用简单的顺序沉淀法制备了两种具有混合组分的CeO₂-ZrO₂材料。用X射线衍射(XRD), 拉曼光谱(Raman), X射线光电子能谱(XPS), 氮气吸附-脱附, 氢气程序升温还原(H₂-TPR)和储氧量(OSC)研究了不同组合形式对负载的单Pd催化剂性能的影响。结果表明, 两个混和组分的催化剂结构和织构性能都得到了改善。由于贵金属和载体材料之间以及载体材料内部各组分之间的强相互作用, 组合的结构促进了Ce³⁺和晶格缺陷的形成, 提高了氧的移动性, 并且相应的催化剂老化前后对于CO、C₃H₈和NO的转化都具有较宽的窗口范围, 说明这种具有混合组分的载体材料在汽油车尾气净化方面具有良好的应用前景。     

用于高性能单Pd三效催化剂的复合组分Ce_xZr_(1-x)O_2材料的制备（英文）

用简单的顺序沉淀法制备了两种具有混合组分的CeO_2-ZrO_2材料。用X射线衍射(XRD),拉曼光谱(Raman),X射线光电子能谱(XPS),氮气吸附-脱附,氢气程序升温还原(H_2-TPR)和储氧量(OSC)研究了不同组合形式对负载的单Pd催化剂性能的影响。结果表明,两个混和组分的催化剂结构和织构性能都得到了改善。由于贵金属和载体材料之间以及载体材料内部各组分之间的强相互作用,组合的结构促进了Ce~(3+)和晶格缺陷的形成,提高了氧的移动性,并且相应的催化剂老化前后对于CO、C_3H_8和NO的转化都具有较宽的窗口范围,说明这种具有混合组分的载体材料在汽油车尾气净化方面具有良好的应用前景。     

Preparation of Ce0.65Zr0.35O2 by co-precipitation： The role of hydrogen peroxide

The effect of H2O2 on the properties of Ce0.65Zr0.35O2 was explored by treating cerium nitrate and zirconium nitrate with a mixed aqueous solution of ammonia and ammonia-carbonate 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-temperature-programmed 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.