铈锆比对储氧材料铈锆固溶体性能的影响

铈锆固溶体作为储氧材料在三效催化剂中起着不可替代的作用。从外围电子排布角度,分析稀土元素铈所具有的独特4f电子层,从结构上探讨铈离子在萤石结构中所起的作用,从而解释了铈作为储氧材料时所发挥的功效,即可在不同的氧气氛下缓冲氧。采用共沉淀法制备了一系列铈锆比不同(Ce/Zr值分别为2/3,1/1,3/2,3/1)的铈锆固溶体,样品经650℃焙烧6 h后,采用X射线衍射(XRD)、比表面积(BET)、程序升温还原(TPR)法、扫描电镜(SEM)分析测定了样品的晶粒度、比表面积、储氧量(OSC),并研究了Zr4+在CeO2晶格的固溶情况。研究发现采用共沉淀法可以成功制备出铈锆比不同的铈锆固溶体,样品具有纳米晶的特征,且XRD谱图显示衍射角随固溶体中Zr4+的增多而增大,由于Zr4+的离子半径小于Ce4+的离子半径,因此随Zr4+的加入产生晶格收缩,晶格常数变小;比表面积数值和储氧能力良好,铈锆比对比表面积和还原性没有显著影响,但储氧量数据却随Zr4+的加入明显增加;Zr4+的加入量对储氧材料固溶度也有影响,当掺杂Zr4+的量较多时,Zr4+会比较容易进入CeO2晶格。     

(Ce-Zr)mA1-mO2复合氧化物的制备及其表征

以碳酸铵为沉淀剂,采用共沉淀法制备铈锆、铈锆镧、铈锆镨复合氧化物,通过X射线衍射(XRD)、BET法和程序升温还原(TPR)等手段对复合氧化物进行了表征,研究了高温焙烧条件下不同铈锆摩尔比和掺杂镧镨对复合氧化物的结构和性能的影响,并初步分析了掺杂La和Pr的作用机理.结果表明, Ce0.76Zr0.24O2在高温焙烧后仍然保持着立方相的固溶体结构,衍射峰没有发生分裂,有着比较好的高温热稳定性;掺杂La和Pr以后均能在一定程度上提高氧化物的热稳定性.     

铈锆复合氧化物的制备及表征

分别采用水热法和共沉淀法制备了铈锆复合氧化物,并对所得的样品进行了XRD,SEM,BET等检测。结果表明,两种方法得到的均是由立方相的Ce0.75Zr0.25O2和四方相的Ce0.5Zr0.5O2组成的复合氧化物。所制备的铈锆复合氧化物均存在中孔结构,水热法制备的样品的比表面积和平均孔径分别为126 m2.g-1和7.3 nm,共沉淀法所得样品的比表面积和平均孔径分别为95 m2.g-1和4.0 nm。     

纳米稀土-锆固溶体的合成及高温稳定性研究

采用共沉淀法制备了RE0.75Zr0.25O2固溶体.通过BET、XRD、SEM/TEM、程序升温还原和氧脉冲吸附等方法对合成产品性能进行了表征.研究了H2O2加入量、水热处理和表面活性剂的浸渍对固溶体高温稳定性的影响,其中水热处理和表面活性剂的浸渍是影响固溶体最终催化性能的关键因素.掺杂镧钇的铈锆固溶体经900℃老化6h后,仍保持单一的立方相结构,比表面积大于60m2·g-1,储氧量达到9.57mL·g-1,显示了较高的比表面积和储氧能力的高温稳定性.     

镨改性铈锆氧化物固溶体的制备与表征

采用溶胶-凝胶法制备了不同比例的Pr掺杂铈锆氧化物固溶体Ce0.6Zr0.4-xPrxO2-y(x=0.05, 0.10, 0.15).X射线衍射证实形成的固溶体为萤石型立方相结构;BET比表面积分析表明,随着Pr的掺杂量由x=0.05递增到x=0.15,在650℃焙烧的样品其比表面积由66.5m2·g-1增加到79.9m2·g-1,而未掺杂样品Ce0.6Zr0.4O2的比表面积为65.1 m2·g-1;粒度分布及透射电镜分析发现,制备的固溶体在水相中存在着团聚现象.应用在含有Pt, Rh和Pd的三效催化剂的制备.催化活性测试表明,在铈锆氧化物储氧材料中掺杂少量Pr,可降低三效催化剂对CO、C3H6和NO的起燃温度.不论是在富燃区还是在贫燃区,所有掺杂Pr的三效催化剂对各气体的催化转化率均高于未掺杂Pr的三效催化剂.     

自模板法制备高热稳定铈锆固溶体

为解决纳米铈锆固溶体高温易烧结、合成过程添加大量表面活性剂、制备步骤繁琐等问题，开发了一种自模板法、不需添加表面活性剂，且操作简单易行的制备高热稳定铈锆固溶体的方法。通过该方法，制备了不同碳酸铵浓度刻蚀得到的铈锆固溶体，并通过XRD、HRTEM、ICP-OES、XPS、N₂吸附脱附测试等表征手段来确认刻蚀步骤对所得铈锆固溶体的影响。结果表明，碳酸铵能选择性地将Ce和Zr的氢氧化物沉淀混合物中的部分Zr刻蚀进溶液中，以此达到在固溶体原位造孔的目的。所得的刻蚀铈锆固溶体在1000℃老化5 h后的比表面积高达30 m²/g,远高于普通共沉淀法制备的具有相同铈锆比的样品，表明碳酸铵刻蚀处理能够提高铈锆固溶体的热稳定性，对高性能铈锆固溶体的可控合成具有较好的指导意义。     

汽车尾气净化催化剂用CexZr1-xO2固溶体的研究进展

综述了 Ce O2 和 Ce XZr1 - XO2 固溶体在汽车尾气净化催化剂中的作用、铈锆氧化物的体相结构及影响铈锆氧化物固溶体储氧能力 (OSC)和织构热稳定性的因素 ,并对其在催化剂中的应用作了简要阐述。     

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。     

制备方法对( Ce0.6Zr0.4O2)0.5(Al2O3)0.5储氧材料性能的影响

分别利用氨水共沉淀法和柠檬酸溶胶-凝胶法制备稀土储氧材料( Ce0.6Zr0.4 O2)0.5(Al2 O3)0.5,并用XRD、BET、H2 - TPR、SEM和EDX等手段研究制备方法对(Ce0.6 Zr0.4 O2 )0.5( Al2O3 )0.5的晶相结构、比表面积、平均孔径、孔容、储氧性能、还原性能、样品各组分含量以及颗粒形貌的影响.结果表明两种方法制备样品均为立方晶相的CeO2 - ZrO2 - Al2 O3固溶体,无Al2O3的晶相.但与氨水共沉淀法比较,柠檬酸溶胶-凝胶法制备样品的比表面积、孔容较大,储氧性、还原性和热稳定性能较高.SEM和EDX测试结果表明,氨水共沉淀法制备样品有明显的聚集现象,而柠檬酸溶胶-凝胶法制备样品的颗粒粒径小,分布均匀,且原子组成更接近理论值.     

不同铝含量及Tw80对铈锆固溶体的影响

为了研究铈锆铝复合化合物(CZ/A)中氧化铝与铈锆固溶体的最佳配比,运用非均匀成核法首先制备了一系列不同Al2O3含量的铈锆铝复合化合物前驱体,之后将其在不同的温度下焙烧。通过比表面积(BET)、X射线衍射(XRD)及H2-TPR等手段,对其织构、高温稳定性、晶型结构及还原等性能进行表征。结果表明,样品的织构性能随着Al2O3含量的增大而增强;但从高温稳定性、单一晶型结构与还原储放氧性能方面看,Al2O3的含量过高,其性能反而会降低。因此,CZ/A性能的增强是Al2O3与铈锆固溶体颗粒间共同作用的结果,且Al2O3的适宜含量为30%～50%(质量分数)。此外,作为分散剂Tw80的添加有助于样品BET的增大及晶粒尺寸的减小,但其添加量也存在适宜的范围,其质量分数以20%～30%为宜。     

Dynamic Oxygen Storage Capacity Measurements on Ceria-Based Material

The constant increase in the number of environ-mental protection regulations worldwide has broughtabout significant restrictions onthe nature and quantityof exhaust gases originating from mobile sources suchas automobile emissions .These increasingly dema…     

Effect of metal doping into Ce0.5Zr0.5O2 on catalytic activity of MnOx/Ce0.5-xZr0.5-xM0.2xOy/Al2O3 for benzene combustion

The research investigated the effect of doping two metals separately or together into Ce0.5Zr0.5O2 on the catalytic activity of MnOx/Ce0.5–xZr0.5–xM0.2xOy/Al2O3 (M=Y, Mn, Y and Mn) for catalytic combustion of benzene. The prepared catalysts were characterized by X-ray diffraction (XRD), surface area analysis, oxygen storage capacity (OSC), and H2-temperature programmed reduction (H2-TPR). Cata-lytic test was performed on a conventional fixed bed flow reactor. The characterization results revealed that Y and Mn ions entered into the ceria-zirconia mixed oxides framework, which improved the textural properties and greatly promoted the MnOx dispersion on the support surface. The complete conversion temperature of benzene on MnOx/Ce0.4Zr0.4Y0.1Mn0.1Oy /Al2O3 was 563 K, and the selectivity of carbon dioxides was 99%. This catalyst could be applied in a wide range of GHSV and wide concentration condition, showing great potential for application.     

Effect of Fe2O3 Loading Amount on Catalytic Properties of Monolithic Fe2O3/Ce0.67Zr0.33O2 -Al2O3 Catalyst for Methane Combustion

Ce0.67Zr0.33O2-Al2O3 solid solution was prepared by the co-precipitation method. Fe2O3-based catalysts supported on the solid solution were obtained by the impregnation method. The article revealed that the optimal loading amount of Fe2O3 on Ce0.67Zr0.33 O2-Al2O3 in our experimental condition for catalytic combustion of methane was 8% （ mass fraction）. The prepared catalysts were characterized by BET, TPR, XRD analyses, and their catalytic activity was investigated after being calcined at 873 K and after being aged in water gas at 1273 K. When the loading amount of Fe203 was 8% （ mass fraction）, the catalyst held the highest activity, and the best temperature speciality and thermal stability. The complete-conversion temperature of methane for fresh and aged sample was 788 and 838 K, respectively. The range between the light-off temperature and the complete-conversion temperature was only 15 K. The characterization results of XRD indicated that Fe2O3 was well dispersed on the Ce0.67Zr0.33O2-Al2O3 matrix. The results of BET and TPR were in good harmony with the catalytic activity results.     

Rare Earth Doping Effects on Properties of Ceria-Zirconia Solid Solution

Ce0.6Zr0.3RE0.1O2(RE=Y, La, Pr, Tb)solid solutions were prepared by co-precipitation technique and characterized by a series of methods. XRD and FT-Raman results show that Ce0.6Zr0.3RE0.1O2 has cubic fluorite structure. The different dopant ion radii bring different effect on the cell parameter of Ce0.6Zr0.3RE0.1O2. The X-ray photoelectron spectroscopy (XPS) results show that the binding energy of Ce3d, Zr3d and O1s for Ce0.6Zr0.3RE0.1O2 rises compared with that for Ce0.6Zr0.4O2, indicating that dopant elements change chemistry environment of solid solutions which is available to improve redox performance. Compared with Pd/Ce0.6Zr0.4O2, doping Y and La does not change air/fuel (A/F) characteristic of TWCs, but doping Pr and Tb widens A/F operating window and makes HC, CO and NO have higher conversion. The light-off temperature of Pd/Ce0.6Zr0.3La0.1O2 is corresponding to that of Pd/Ce0.6Zr0.4O2. However, the light-off temperatures of Pd/Ce0.6Zr0.3M0.1O2 (M=Y, Pr, Tb) are lower than that of Pd/Ce0.6Zr0.4O2, which keep much lower after high temperature treatments. Among Pd/Ce0.6Zr0.3RE0.1O2, Pd/Ce0.6Zr0.3Tb0.1O2 represents wider A/F operating window, higher conversion, lower light-off temperature and better high-temperature resistance.     

Effect of PdO_x structure properties on catalytic performance of Pd/Ce_(0.67)Zr_(0.33)O_2 catalyst for CO,HC and NO_x elimination

Pd/Ce_(0.67)Zr_(0.33)O_2 catalyst was pretreated in different atmosphere respectively, and characterized by CO chemical adsorption, XPS, HR-TEM, H_2-TPR, Raman, OSC and in situ DRIFTS to investigate the effect of the structure properties of PdO_x species on the catalytic performance for CO, HC and NO_x elimination. The results show that Pd/CZ catalyst pretreated in air atmosphere has higher oxidation activity of HC due to having high Pd dispersion and strong interaction between PdO_x and CZ support. Pd/CZ-H catalyst pretreated in reducing atmosphere exhibits better catalytic performance of NO_x elimination because of having relatively big Pd particle size, more Pd species in metallic state and higher concentration of oxygen vacancies. While for the Pd/CZ-RG catalyst pretreated in reactant atmosphere, strong adsorption of HC species on the surface of catalysts would lead to a part of active sites being covered, which inhibits HC and NO conversions.     

Quaternary Oxide of Cerium, Terbium, Praseodymium and Zirconium for Three-Way Catalysts

Inthelastdecadethethree waycatalystshave beenremarkablyimproved.Oxygenstoragecapacity(OSC)ofthecatalystwasdeterminedbyTPR.The measuredvalueisactuallyapartoftheoxygentransfer capacity(OTC)offluorite typeoxidescontainingCe,and orPr,and orTb[1,2].Theseoxides,Ce1-x-y PrxTbyO2-δ(0≤x≤1,0≤y≤1,0≤δ≤0.5)can releasetheirlatticeoxygenwhenthetemperatureisin creasedunderdifferentoxygenpartialpressureinclud inghydrogenflow,buttheywillabsorboxygenfromits vicinityenvironmentwhenthetemperatureisde…     

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.     

Effects of loading transition metal(Mn,Cr,Fe,Cu) oxides on oxygen storage/release properties of CeO_2-ZrO_2 solid solution

Cerium zirconium-based(CZ) oxygen storage materials(OSMs) play a crucial role in three-way catalysts(TWCs),while CZ needs to be modified to satisfy more rigorous emission standard.In this study,transition metal(TMs=Mn,Cr,Fe,Cu) oxides modified CZ were prepared by incipient wetness impregnation method to improve the oxygen storage capacity of CZ-based materials.To clearly illustrate the influence of TM oxides,N_2 adsorption-desorption,X-ray diffraction(XRD),oxygen storage capacity(OSC),temperature programmed reduction by H_2(H_2-TPR) and X-ray photoelectron spectroscopy(XPS) were used to characterize the physical and chemical properties of samples.It is found that,all modified CZ have higher OSC,lower reduction temperatures than those of pristine CZ.Interaction between TMOs and CZ take precedence over specific surface to influence OSC.Notably,FeO_x/CZ has the highest OSC,which is about 1.9 times that of CZ and it could be attributed to synergistic effect between FeO_x and CZ;CuO_x/CZ has the lowest reduction temperature which is 168℃lower than that of CZ,and it can be explained by hydrogen spillover effect.     

Catalytic combustion study of soot on Ce0.7Zr0.3O2 solid solution

The Ce0.7Zr0.3O2 solid solution and CeO2 were prepared using the sol-gel method. The phase structure, crystallite sizes and the reducibility of the catalysts were characterized by XRD and H2-TPR techniques. XRD results indicated that Zr^4＋ had replaced part of Ce^4＋ to form a fluorite-like solid solution, which was favorable to obtain ultrafine nanoparticles. The ratio of main HE consumption for Ce0.7Zr0.3O2：CeO2 was 4.4：1.0, implying that the solid solution could improve the reducibility compared to the single CeO2. The Ce0.7Zr0.3O2 solid solution catalyst showed a sharp combustion peak at 397 ℃, which was 200 ℃ lower than that of the single soot. The good catalytic activity of the Ce0.7Zr0.3O2 was attributed to the formation of nano-CeO2-based solid solution, which enhanced the reducibility and then improved the combustion activity. As Ce0.7Zr0.3O2 could be easily reduced to Ce0.7Zr0.3O2-x meanwhile, after oxygenation, the Ce0.7Zr0.3O2.x was recovered to Ce0.7Zr0.3O2 completely. A catalytic combustion reaction mechanism was proposed： the Ce0.7Zr0.3O2 was reduced to Ce0.7Zr0.3O2-x by the reaction with carbon and then it was recovered to Ce0.7Zr0.3O2-x by the interaction with O2.     

Study of cerium ion in (Y0.95La0.05)2O3:Ce

(Y0.95La0.05)2O3: Ce3+ nano-powder was synthesized by co-precipitation method and sintered at 800 and 900 oC. All the samples were cubic phase characterized by X-ray diffraction (XRD) analysis. The samples sintered at the lower temperature exhibited luminescence. According to the distinguishable structure of Ce 3d peaks and the shift of O 1s lines in the X-ray photoelectron spectroscopy (XPS), luminescence was further confirmed to originate from Ce3+ ions. Effects of introducing La3+ into Y2O3 were discusse...