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 Manganese Doping on Oxygen Storage Capacity of Ceria-Zirconia Mixed Oxides

CeO2-ZrO2-MnOx mixed oxide series were prepared by sol-gel method. CO pulse and CO-O2 cycle measurements were carried out to examine the oxygen storage complete capacity （OSCC） and dynamic oxygen storage capacity （OSC） of the samples. The doping method brought about strong interactions between manganese oxide and ceria, both in the bulk and on the surface. Only a small part of Mn cations are incorporated into the ceria lattice to form solid solutions and the remaining are left on the surface as finely dispersed Mn3O4. The OSC behaviors of the materials are influenced by the doping amount of Mn and the solubility of Mn in the CeO2 lattice. The OSC is more easily affected by available contents of oxygen storage components when the measurement frequency is low. Comparatively, the concentration of lattice defects, which affects the mobility of bulk oxygen, is the determining factor under high frequency.     

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.     

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…     

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.     

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.     

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.     

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。     

Synthesis, Structure and Luminescent Properties of a Nine-Coordinated Praseodymium Complex

The Pr (TFA) 3phen ( C2H5OH ) quarternary complex with 2-thenoyhrifluoro-acetone ( TFA ), 1,10phenanthroline(phen) and ethanol were synthesized and characterized by single-crystal X-ray diffraction. The central Pr^3 ion is nine-coordinated. The infrared (IR)spectrum, diffuse reflectance (DR)spectrum and fluorescence measurements of the complex were investigated.     

Study on Separation of Lanthanum from Praseodymium Complexes with IMDA by Gel and Macroporous Anion Exchangers

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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.     

Influence of Additives Ceria and Lanthana on Performance of Pd／Al／Monolith Honeycomb Catalysts

The effects of ceria and lanthana additives on activity and thermal stabilization of the catalysts for CO oxidation were studied. The results show that the addition of CeO2 clearly improves the catalytic activity, which may derive from the synergic effect between CeO2 and PdO. The catalysts were characterized by means of temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS) measurements. The XPS results of a slight increase in metal oxidation state reflect that the charge transfers from metal to ceria and ceria is slightly reduced, which leads to a decrease of the Ce-O bond strength. Pd-Ce synergism affects the reduction behavior of the catalysts. The TPR results show that the CeO2 ad-dition lowers the reduction temperature of PdO, while palladium facilitates the reduction of the ceria. For PdO/La2O3/Al2O3/monolith honeycomb catalysts, the aging test measurements at 1050 ℃ and the XRD results show that the formation of LaAlO3 which neutralizes the surface alumina defects inhibits the sintering of alumina.     

Oxides Catalysts of Rare Earth and Transient Metal for Catalytic Oxidation of Benzene

The catalysts of CeO2 and the mixture of CeO2 and CuO were prepared, and the activities of these catalysts for completely oxidizing benzene were studied.The results show that the optimal proportion of CeO2/CuO is 6: 4.The highest temperature at which benzene was completely oxidized on these catalysts at different airspeed was measured.Compared these catalysts with the noble metal used, our catalysts had superiority in the resources and the industrial cost besides good activities.     

Preparation and characteristics of nano-crystalline Cu-Ce-Zr-O composite oxides via a green route: supercritical anti-solvent process

The nano-crystalline Cu-Ce-Zr-O composite oxides were successfully prepared by the supercritical anti-solvent (SAS) process. The physicochemical properties and catalytic performances were investigated by X-ray diffraction (XRD), Raman spectroscopy, H2 temperature-programmed reduction (H2 -TPR), oxygen storage capacity (OSC) measurement and catalytic activity evaluation. It was found that Cu2+ ions incorporated into CeO2 -ZrO2 lattice to form Cu-Ce-Zr-O solid solution associated with the formation of oxygen vacancies. The Cu-Ce-Zr-O catalysts prepared via the SAS process with the Cu content 2.63 mol.% showed the highest OSC index of 636.9 μmol/g. Compared with the samples prepared by impregnation method, Cu doping using SAS process could improve the dispersion of Cu2+ in the composite oxide, enhance the interaction between Cu2+ and CeO2-ZrO2 , improve the reducibility of catalyst, and thus improve the OSC performance and increase the catalytic activity for CO oxidation at low temperature.     

电感耦合等离子发射光谱法测定镨钕金属及其氧化物中15个稀土元素的配分量

用电感耦合等离子发射光谱法测定镨钕金属及其氧化物中15个稀土元素的配分量。本方法镨钕回收率99％-100．4％，相对标准偏差小于1％，其余13个稀土元素回收率90％～110％，相对标准偏差小于5％。     

Thermogravimetric Study on Oxygen Adsorption/Desorption Properties of Double Perovskite Structure Oxides REBaCo2O5+δ (RE= Pr, Gd, Y)

The oxygen adsorption/desorption properties of double perovskite structure oxides PrBaCo2O5+δ, GdBaCo2O5+δ, and YBaCo2O5+δ were investigated by the thermogravimetry (TG) method in the temperature range of 400～900 ℃. The calculated oxygen adsorption/desorption surface reaction rate constants ka and kd of these double perovskite structure oxides were larger than the commonly used cubic perovskite oxides, such as Ba0.95Ca0.05Co0.8Fe0.2O3-δ and Ba0.5Sr0.5Co0.8Fe0.2O3-δ, whereas, the oxygen permeation flux was comparable to that of the latter, which was attributed to the smaller difference of oxygen vacancy in oxygen and nitrogen atmosphere (Δδ/Vmol) in these double perovskite structure oxides. The large oxygen adsorption/desorption rate constants of GdBaCo2O5+δ and PrBaCo2O5+δ made them nice catalyst coating materials, on other membrane surfaces, to improve the oxygen permeability.     

In situ photoemission study of interface and film formation during epitaxial growth of Er2O3 film on Si(001) substrate

Synchrotron radiation photoemission spectroscopy was used to study the formation process of Er2O3/Si(001) interface and film during epitaxial growth on Si. A shift in the O core-level binding energy was found accompanied by a shift in the Er2O3 valence band maxi-mum. This shift depended on the oxide layer thickness and interfacial structure. An interfacial layer was observed at the initial growth of Er2O3 film on Si, which was supposed to be attributed to the effect of Er atom catalytic oxidation effect.     

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 modified CeO2-ZrO2 was impregnated with 1 wt.% Pd to prepare the catalysts.The structure and reducibility of the fresh and hydrothermally aged catalysts were characterized by X-ray diffraction(XRD),Raman,X-ray photoelectron spectroscopy(XPS),CO chemisorption 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.     

Temperature Programmed Reduction Studies on CeO2-Containing Catalysts

Temperature programmed reduction (TPR) study was carried out for CeO2/A12O3 and CeO2/ZrO2 catalysts to evaluate oxygen storage property induced by a facile redox cycling of Ce ion. The CeO2/ZrO2 catalyst possesses excellent oxygen storage activity at 373 K after reduction above 1173 K although the oxygen storage of CeO2/Al2O3 catalyst after reduction above 1173 K is poor because of the formation of CeAlO3. Consequently, the oxygen storage on the CeO2/ZrO2 catalyst smoothly occurs from low temperatures when the catalyst is reduced even at high temperatures.     

Effect of Annealing on Rare Earth Based Hydrogen Storage Alloys

Rare earth-based hydrogen storage alloy used as negative electrode materials for nickel-metal hydride (Ni-MH) batteries are used commercially.The effect of annealing treatment with different annealing temperature and time on the MLNi3.68 Co0.78 Mn0.35 Al0.27 and MMNi3.55 Co0.75 Mn0.40 Al0.30 alloys were investigated.The crystal microstructure,pressure-composition-isotherms (p-C-T) and electrochemical properties of alloys were examined by X-ray diffraction (XRD), automatic PCI monitoring system and electrical performance testing instruments.The optimum annealing treatment conditions of two kinds of alloys were determined.