喷动床内纳米颗粒气固两相流动的数值模拟

采用欧拉-欧拉双流体模型,颗粒动理学理论模拟颗粒相流动,采用周涛和李洪钟(1999)的力平衡模型预测纳米颗粒聚团尺寸,对喷动床内纳米颗粒聚团流化过程进行了数值模拟,得到了喷动床内纳米颗粒聚团的流化过程,获得喷射区和环隙区内颗粒相速度和浓度分布。分析了喷动床结构和进口气体速度等对纳米颗粒聚团流化特性的影响。由于纳米颗粒的特殊性质,不易形成喷泉区。适当的喷动床结构和进口气体速度有助于形成稳定喷动。     

In Situ Investigation of Methane Dry Reforming on Metal/Ceria(111) Surfaces: Metal–Support Interactions and C−H Bond Activation at Low Temperature

Studies with a series of metal/ceria(111) (metal=Co, Ni, Cu; ceria=CeO₂) surfaces indicate that metal–oxide interactions can play a very important role for the activation of methane and its reforming with CO₂ at relatively low temperatures (600–700 K). Among the systems examined, Co/CeO₂(111) exhibits the best performance and Cu/CeO₂(111) has negligible activity. Experiments using ambient pressure X‐ray photoelectron spectroscopy indicate that methane dissociates on Co/CeO₂(111) at temperatures as low as 300 K—generating CH_x and CO_x species on the catalyst surface. The results of density functional calculations show a reduction in the methane activation barrier from 1.07 eV on Co(0001) to 0.87 eV on Co²⁺/CeO₂(111), and to only 0.05 eV on Co⁰/CeO_2−x (111). At 700 K, under methane dry reforming conditions, CO₂ dissociates on the oxide surface and a catalytic cycle is established without coke deposition. A significant part of the CH_x formed on the Co⁰/CeO_2−x (111) catalyst recombines to yield ethane or ethylene.     

Challenges in the use of density functional theory to examine catalysis by M‐doped ceria surfaces

For CeO₂ or M‐doped CeO₂ catalysts, reliable energetics associated with surface reactivity requires accurate representation of oxidized and reduced metal states. Density functional theory (DFT) is used extensively for metals and metal oxides; however, for strongly correlated electron materials, conventional DFT fails to predict both qualitative and quantitative properties. This is the result of a localized electron self‐interaction error that is inherit to DFT. DFT+U has shown promise in correcting energetic errors due to the self‐interaction error, however, its transferability across processes relevant to surface catalysis remains unclear. Hybrid functionals, such as HSE06, can also be used to correct this self‐interaction error. These hybrid functionals are computationally intensive, and especially demanding for periodic surface slab models. This perspective details the challenges in representing the energetics of M‐doped ceria catalyzed processes and examines using DFT extensions to model the localized electronic properties. © 2013 Wiley Periodicals, Inc.     

Structural and catalytic properties of lanthanide (La, Eu, Gd) doped ceria

Ce_0.9M_0.1O_2−δ mixed oxides (M=La, Eu and Gd) were synthesized by coprecipitation. Independent of the dopant cation, the obtained solids maintain the F-type crystalline structure, characteristic of CeO₂ (fluorite structure) without phase segregation. The ceria lattice expands depending on the ionic radii of the dopant cation, as indicated by X-ray diffraction studies. This effect also agrees with the observed shift of the F_2g Raman vibrational mode. The presence of the dopant cations in the ceria lattice increases the concentration of structural oxygen vacancies and the reducibility of the redox pair Ce⁴⁺/Ce³⁺. All synthesized materials show higher catalytic activity for the CO oxidation reaction than that of bare CeO₂, being Eu-doped solid the one with the best catalytic performances despite of its lower surface area.     

双模板法制备具有介孔孔壁的三维有序大孔二氧化铈及其改善的低温还原性能

以聚甲基丙烯酸甲酯(PMMA)为硬模板,三嵌段共聚物F127、十六烷基三甲基溴化铵(CTAB)或聚乙二醇(PEG)为软模板剂(表面活性剂),柠檬酸为络合剂,硝酸铈为金属前驱体,采用双模板法成功地合成出具有介孔孔壁的三维有序大孔(3DOM)结构的立方相CeO2样品CeO2-F127,CeO2-CTAB和CeO2-PEG,...     

用于质子交换膜燃料电池抗CO的Pt-CeO2/C催化剂的制备和表征

采用一步沉淀法,制备了纳米级Pt-CeO2/C电催化剂.透射电镜和X射线衍射表征结果表明,制备的催化剂Pt颗粒均匀分散于碳载体表面,其粒径主要分布于1.5～2.5 nm.将Pt-CeO2/C催化剂制备成质子交换膜燃料电池膜电极,经循环伏安和单电池极化曲线测试发现,Pt-CeO2/C催化剂性能与Pt/C催化剂的相当.一氧...     

TA of non-stoichiometric ceria obtained via hydrothermal synthesis

Doped ceria was studied in the last 20 years as a solid electrolyte capable of replacing stabilized zirconia in fuel cells. Nevertheless, one of the problems concerned with the application of this material is the joint presence of the Ce(III) and Ce(IV) in the ceria sublattice, mainly under low partial pressure of oxygen. TG and DTA measurements were performed in order to verify non-stoichiometric character for cerias hydrothermally treated under reflux and in autoclave. X-ray powder diffraction was used to observe long-range structural evolution varying time and temperature of reaction and the type of hydrothermal synthesis. Finally, scanning electron microscopy (SEM) gave the temperature influence for powder morphology. Those techniques pointed out that: i) reaction temperature is not important for converting Ce³⁺ to Ce⁴⁺; ii) testing the reaction time parameter, it is observed quite complete oxidation for the 2-12 h range; and iii) the type of hydrothermal synthesis parameter influences the crystallinity and non-stoichiometric character of products. This revised version was published online in August 2006 with corrections to the Cover Date.     

UV absorption properties of ceria-modified compositions within the fluorite-type solid solution CeO2-Y6WO12

A new fluorite-type solid solution domain has been evidenced in the system (1−x) CeO₂−x/7 Y₆WO₁₂□₂ using the amorphous citrate route. All the studied phases (0?x?1) crystallize in a cubic-type symmetry. Diffuse reflectance spectra reveal a strong optical absorption between 380 and 400 nm. All substituted compositions spectral selectivities are estimated suitable for application as inorganic UV absorbers. The non linear variation observed in the optical gap values between Y₆WO₁₂ and CeO₂ is attributed to the presence of the cerium 4f-block band. Additionally, Time Resolved Microwave Conductivity (TRMC) experiment and phenol photodegradation analyses carried out on the Ce_0.81Y_0.16W_0.03O_1.95□_0.05 (x=0.19) composition do not indicate any photocalatytic activity for this material.     

Catalytic decomposition of cyclohexanol over molybdena doped ceria catalysts

Summary Molybdena modified pure as well as sulfated ceria systems have been studied with a view to investigate their structure, surface acidic properties and catalytic behavior for cyclohexanol decomposition reaction. The characteristics of the modified systems were obtained from XRD measurements and acid structural properties from Temperature Programmed Desorption (TPD) of ammonia.     

Nano hillock and complex crater formation by low-energy proton implantation with incident angle into lithium niobate single crystal

The formation of nano-size hillocks and simple and complex craters was observed as a result of ion–surface collisions with a lithium niobate single crystal on proton implantation. The low-energy ion implantation process is considered as a controllable and versatile tool for surface and near-surface modifications down to an atomic scale as an alternative to the swift heavy ion irradiation effect. Lithium niobate samples implanted by proton ions with a low energy of 120 keV at various fluences (10¹⁵ and 10¹⁶ protons/cm²) were studied using atomic force microscopy (AFM). The images of surface modification appear as simple and complex crater formation in the case of incident ions at normal to the surface. Varying the angle of incidence to θ=30° with respect to the normal to the surface, hillocks and multi-hillocks were observed. The complex craters with central uplifted, cone-shaped hillocks with a height of up to 4.3 nm are surrounded by low-height (1 nm) rims. The hillock height varies from a few nanometers to 16 nm with the basal diameter from 200 to 340 nm depending on the ion implantation conditions. The complex crater and hillock formation on the lithium niobate sample surface at the collision spot with the impact of incident angle is discussed.