钇掺杂对Ce0.33Zr0.67O2储氧性能的影响

采用柠檬酸溶胶凝胶法制备了一系列钇掺杂的富锆铈锆复合氧化物Ce0.33YxZr0.67-xO2,并通过XRD,BET,OSC,XPS,in-situ CO-FTIR等测试,系统研究了钇掺杂后铈锆复合氧化物储放氧性能的变化规律及其影响因素。结果表明,钇离子能够进入铈锆晶格形成固溶体,并提高铈锆体系的结构热稳定性。对于新鲜样,钇掺杂可大幅提升Ce0.33Zr0.67O2材料的比表面积,提高单位质量铈锆材料的储氧能力;但老化后,钇掺杂样品的储氧性能随着掺杂量的增加而减小。通过XPS及原位红外吸附性能测试证实,钇在Ce0.33Zr0.67O2材料表面主要取代锆离子,其掺杂会降低样品的表面吸附能力,抑制铈的氧化还原反应,从而导致该体系储氧性能的下降。     

Role of Surface Adsorption in Fast Oxygen Storage/Release of CeO2 -ZrO2 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.     

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…     

Oxygen Storage Capacity and Adsorptive Property of Praseodymium Oxides

Ceriumoxideisusedwidelyinthree waycatalystduetoitsoxygenstoragecapabilitywhichenablesthecatalysttooperatemoreefficientlybymakingitlesssensitivetothevariationofoxygenconcentrationinex haustgasstream[1～ 3] .TheoxygenstoragecapabilityofceriastemsfromthevalencechangebetweenCe3+andCe4 +[1,2 ] .Thereareafewotherelementswithvariableoxidationstatewithinthewholeseriesofrareearth .Praseodymiumisoneoftheelementswhichcanformaspectrumofoxygen deficientornonstoi chiometricPrOx.Ontheotherhand ,theproperti…     

A rationale for the development of thermally stable nanostructured CeO2-ZrO2-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.     

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.     

Study on Catalysts with Rhodium Loading on Different Cerium-Zirconium Mixed Oxides

The catalysts with Rh loading on different cerium-zirconium mixed oxides were characterized by BET, H2-TPR and OSC. The effects of different cerium-zirconium mixed oxides on catalytic performance and thermal stability of Rh loaded catalyst were studied. The results show that: (1) Rh can enhance cerium-zirconium mixed oxides OSC and catalytic reaction rates; (2) cerium-zirconium mixed oxides with high Ce contents and low Zr contents are more favorable to the stability of catalysts. Moreover, the contents of CeO2 have important effect on catalysts characteristics, and the addition of some rare earth components, such as La, Pr and Nd also have some influences.     

Dynamic Oxygen Storage Opacity 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 of Pt-, Pd-, Rh/CeO2-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.     

Effects of ZrO2 Content on Structure and Performance of Cu/CeO2-ZrO2 Catalysts for Water-Gas Shift Reaction

Water-gas shift(WGS)is a critical step in fuelprocessors for preli minary COclean-up and additionalhydrogen generation prior to the CO clean-up stage,which opened up new potential applications for WGScatalysts.Recently several formulations of noble-met-al…     

Structure and Catalytic Behavior of CuO-ZrO-CeO2 Mixed Oxides

The effect of doping CuO on the structure and properties of zirconia-ceria mixed oxide was studied. The results show that addition of CuO decreases the reduction temperature of ceria, and stabilizes the cubic structure of mixed oxides, and enhances catalytic activity of CuO-ZrO-CeO2 mixed oxides for CO oxidation. Increasing ceria content in the mixed oxides can enhance the catalytic activity, but some impurities such as sulfate make catalytic activity falling. There is little effect of calcination temperature on catalytic activities, implying that these catalysts are effective with good thermal stability.     

Influence of Supports on Catalytic Performance and Carbon Deposition of Palladium Catalyst for Methane Partial Oxidation

The catalytic performance of methane partial oxidation was investigated on Pd/CeO2-ZrO2 and Pd/α-Al2O3 catalysts.The catalysts were characterized by XRD,Raman spectra,and TG-DTA techniques.The results show that CeO2-ZrO2 support is more advantageous for the catalytic activity and stability of catalysts compared to α-Al2O3.TG-DTA and Raman spectra results indicated that carbon deposited on the catalysts was in the form of graphite,which is the main reason for the deactivation of catalysts after a 24-hour reaction.Moreover,CeO2-ZrO2 had positive effect on inhibiting carbon deposition.     

Preparation and Characterization of CeO2-ZrO2 Solid Solution Ultrafine Particles Using Reversed Microemulsion

The development of the TWCs (three-way cata-lysts) was dictated bythe need to si multaneously con-vert the three main pollutants inthe exhaust gases ,i .e .,hydrocarbons (HCs) ,COand NOxpresent in theautomotive exhaust to H2O, CO2and N2[1]. Highestconvers…     

Distribution of Cerium Ion in Cordierite Ceramics and Its Effect on Structure of Cordierite Crystal

Cerium addition plays an important role in sintering, transformation and phasicochemical properties of cordierite ceramics. The present work aims at studying the distribution of Ce4+ in cordierite ceramics and its effect on the structure of cordierite crystal by means of differential thermal analysis (DTA), X-ray diffraction (XRD) and scanning electronic microscope (SEM) so as to clarify the behavior of Ce4+. Results show that Ce4+ can exist in two forms of CeO2 particles and solid solution in Ce4+ -modified cordierite ceramics by the sol-gel method. The CeO2 particles separately distribute in the cordierite matrix. Ce4+ dissolves little into cordierite crystal, resulting in a decrease of lattice constants ofthe crystal. This kind of distribution behavior of Ce4+ makes us to easily tailor the properties of the cordieritc ceramics.     

Effect of Preparation Method on Surface Area and Crystalline Form of CeO2-ZrO2 Solid Solution

TheCeO2 ZrO2 solidsolutionisacrucialcompo nentinthethree waycatalysts(TWCs)usedtocatalyzethesimultaneouspurificationofCO ,HCandNOxfromanautomobileexhaust [1～ 3] .Besidesafeasiblecatalyticactivity ,itshouldhavehighthermalstabilityandoxygenstoragecapacity(OSC) .InordertogainhighperformanceCeO2 ZrO2 solidsolution ,varioustechniqueshavebeendeveloped .ItwasshownthataneffectofpreparationmethodonthesurfaceareaandcrystallineformofCeO2 ZrO2 isveryobvious .Intheearliestwork ,theCeO2 ZrO…     

灼烧过程对稀土氧化物中氯元素的影响

研究稀土氧化物制备过程中灼烧过程对最终稀土氧化物中氯的影响,考察了碳酸盐灼烧时的装填量与装填方式、灼烧温度、升温曲线等对最终稀土氧化物中氯的影响。结果表明,在碳酸盐非金属(氯离子含量)元素含量一定的条件下,碳酸盐的装料越少、升温速度越慢、灼烧温度越高,最终产出的稀土氧化物的氯含量就越低。     

Catalysis of Ce_xZr_(1–x)O_2 for di-iso-propyl-ether hydration

The catalytic potential of CexZr1–xO2 in isopropyl ether(DIPE) hydration was explored. While the acidic H-zeolite catalyst was favorable for propylene formation through carbenium ion mechanism, Ce-ZSM-5 and CexZr1–xO2 catalysts improved product selectivity of isopropyl alcohol(IPA) through redox mechanism. The catalytic property of CexZr1–xO2 depended on the preparation method and variable, type of cerium precursor and Ce/Zr ratio. By means of characterizations with X-ray diffraction, N2 adsorption isotherms and NH3 temperature programmed desorption, tetragonal phase of CexZr1–xO2 was proposed as the active phase in which CeO2 and ZrO2 catalyzed synergistically the DIPE hydration with IPA product selectivity. The CexZr1–xO2 prepared from cerium sulfate precursor with co-precipitation hydrothermal method exhibited maximum catalytic activity and IPA product selectivity. The precursor effect was attributed to the stabilization of SO42– species on the tetragonal phase of CexZr1–xO2 and super solid acidity.     

CexZr1-xO2储氧材料制备方法研究进展

本文综述了共沉淀法、溶胶-凝胶法、水热法、高能球磨法等常用CexZr1-xO2储氧材料的合成方法,并进行了比较.阐述了CexZr1-xO2的基本改性机制,详述了稀土元素、碱土元素以及过渡金属对CexZr1-xO2的改性效果及原理.相关研究结果表明,CexZr1-xO2晶体结构、形貌、比表面积与其合成方法有很大关系,从而...     

Ce_xTi_(1-x)O_2 Mixed Oxides Supported CuO Catalyst for NO Reduction by CO

Uptodate ,numerousstudieshaveshownthatrareearthoxidesaretheexcellentstructuralandelec tronicpromoterstoimprovetheactivity ,selectivityandthermalstabilityofcatalysts[1,2 ] .Themostwidelyappliedrareearthoxideinindustrialcatalysisiscer tainlyCeO2 .However ,amajordrawbackofCeO2 isthelossofoxygenstoragecapability (OSC)duetoitssinteringathighertemperature (>75 0℃ ) ,whichleadstothedeactivationofthecatalyst[3 ,4] .Oneap proachpreviouslyusedtostabilizeceriaagainstsinter ingwastodopeitwithotheranti…