Zn-Cr整体催化剂中Ce-Zr溶胶涂层的制备、表征及对甲醇自热重整反应的影响

 以溶胶-凝胶法制备出粒子尺度均一的Ce-Zr溶胶. TEM和XRD结果表明, 1073 K焙烧后, Ce-Zr复合氧化物的粒径仍保持在20～50 nm. 将Ce-Zr溶胶作为甲醇自热重整制氢Zn-Cr整体催化剂的涂层,考察了溶胶在涂层多次重复过程中的稳定性和干燥方式对Ce-Zr涂层龟裂程度的影响. 结果表明,对多次使用后的溶胶进行胶溶处理可以有效控制涂层制备过程中胶体粒子的大小; 微波干燥更加有利于蜂窝陶瓷载体各通道中Ce-Zr涂层的均匀干燥; Ce-Zr涂层的引入显著提高了甲醇自热重整Zn-Cr整体催化剂的稳定性,这归因于Ce-Zr涂层提高了催化剂的氧化还原活性,使其能量匹配更好,避免了热点的产生,从而抑制了催化剂的烧结与失活.     

Microstructural studies of bulk and thin film GDC

Ceria rare earth solid solutions are known as solid electrolyte with potential application in oxygen sensors and solid oxide fuel cells. We report the preparation of gadolinia-doped ceria, Ce_0.90Gd_0.10O_1.95, by the conventional solid-state reaction method and the preparation of thin films from a sintered pellet of gadolinia-doped ceria by the pulsed laser deposition technique. The effect of process conditions, such as substrate temperature, oxygen partial pressure, and laser energy on microstructural properties of these films are examined using powder X-ray diffraction, scanning electron microscopy, atomic force microscopy, and Raman spectroscopy.     

Oxygen Storage Materials for Automotive Catalysts: Ceria-Zirconia Solid Solutions

This paper reviews progress in the development of oxygen storage materials for automotive exhaust catalysts. The research was mainly conducted as a study and development exercise in the author's laboratory in Japan.Ceria-lanthana solid solutions (CL) and the first generation of ceriazirconia solid solutions (CZ) were developed as excellent oxygen storage materials for automotive catalysts in the 1980s. These materials consist of ceria doped with less than 20 mol% of La⁴⁺ or Zr⁴⁺. An increase in oxygen defects in CL and CZ under reductive conditions is responsible for an enhanced oxygen storage capability on the cerium atoms. An accurate measure of the oxygen storage capacity (OSC) per cerium is very important for theoretical and practical treatments of the catalyst. The term partial OSC was introduced to describe this capacity and to differentiate it from the usual definition of the OSC, known also as the total OSC. After the development of CL and CZ, a new technology was developed to dissolve more than 20 mol% of zirconia in the ceria, allowing second generation CZ and third generation CZ (known as ACZ, which is doped with alumina) to be successfully developed in the 1990s. The partial OSC of these materials increases with increasing amounts of zirconia dissolved in the ceria, and also with decreasing material particle size after an engine durability test. In the case of ACZ, alumina was added to CZ based on the diffusion barrier concept, in which a diffusion barrier layer inhibits the coagulation of CZ and A when the material is required for duty at high temperature in air.Furthermore, the relationship between the total or partial OSC and the structure of the ceriazirconia solid solutions is explained in this paper.For ceriazirconia solid solutions composed of equimolar CeO₂ and ZrO₂(Ce/Zr=1), the total or partial OSC of the -phase CeZrO₄, in which the cerium and zirconium ions are regularly distributed, was about twice as large as that of a ceriazirconia solid solution with a relatively irregular distribution of cerium and zirconium ions, and about five times larger than that of a mixture of ceria powder and zirconia containing only a small amount of ceriazirconia solid solution. It corresponds to about 89% of the theoretical maximum value.For a ceriazirconia solid solution composed of non-equimolar CeO₂ and ZrO₂(Ce/Zr 1), the partial OSC of a ceria--phase solid solution with a zirconia content of between 30 and 50mol% is much higher than that of a ceriazirconia solid solution of the same zirconia content. The partial OSC of a -phase and zirconia mixed oxide, which is formed by reducing the material at 1200 °C, reaches a value above 0.20 mol-O₂/mol-Ce (about 80% of the theoretical maximum value of the partial OSC), when the zirconia content is between 50 and 80 mol%.The Toyota Motor Corp. has put automotive three-way catalysts containing the first, second and third generations of CZ into practical use on a global basis.     

Nano-ionic thin films of gadolinia-doped ceria prepared by pulsed laser ablation

Microstructural properties of nano-ionic thin films of gadolinia-doped ceria (GDC) prepared by pulsed laser ablation from sintered targets of gadolinia (5–20 mol%) doped ceria are investigated. The ionic conductivity measurements of the sintered pellets showed a decrease in the activation energy from 1.1 to 0.65 eV for 5 and 30 mol% gadolinia-doped ceria, respectively. The microstructural properties of the GDC films as a function of substrate temperature, oxygen partial pressure, and laser energy show that the films are polycrystalline in the entire range of substrate temperature. The grain size is found to increase with increasing temperature up to 873 K. Further improved crystallinity is noticed for the films grown with oxygen partial pressure of 0.1–0.2 mbar. X-ray diffraction and transmission electron microscopy (TEM) reveal nanocrystalline grains with textured growth along <111> orientation in these films at low substrate temperature and at lower oxygen partial pressure. TEM study shows a uniform distribution of nanocrystal of 8–10 nm for energies ≤200 mJ/pulse, and nanocrystals embedded in a large crystalline matrix of doped ceria for energies in the range 400–600 mJ/pulse. Raman spectroscopy also confirms the defects in these films. The study also reveals that the substrate temperature and oxygen partial pressure could influence preferred orientation, while the laser energy could significantly influence defect concentration in these films. Invited paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

Low temperature processing of dense samarium-doped CeO<Subscript>2</Subscript> ceramics: sintering and intermediate temperature ionic conductivity

Samarium-doped Ceria powders for solid electrolyte ceramics were synthesized by a combustion process. Cerium nitrate and samarium nitrate were used as the starting materials, and glycine was used as fuel. Decomposition of unburned nitrogen and carbon residues was investigated by simultaneous thermogravimetry analysis and differential thermal analysis experiments. The X-ray diffraction results showed that the single-phase fluorite structure forms at a relatively low calcination temperature of 800 °C. X-rays patterns of the SDC powders revealed that the crystallite size of the powders increases with increasing calcination temperature. The sintering behavior results showed that more than 96% of the relative density is obtained for powders sintered at 1,100 °C for 8 h. The alternating current impedance spectroscopy results showed that the SDC15 sample sintered at 1,100 °C has ionic conductivity of 0.015 Scm⁻¹at 650 °C in air. The present work results have indicated that glycine–nitrate route is a relatively low-temperature preparation technique to synthesize SDC powders with a high sinterability and a good ionic conductivity. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

Active Exsolved Metal–Oxide Interfaces in Porous Single-Crystalline Ceria Monoliths for Efficient and Durable CH4/CO2 Reforming

Dry reforming of CH₄/CO₂ provides an attractive route to convert greenhouse gas into syngas; however, the resistance to sintering and coking of catalyst remains a fundamental challenge at high operation temperatures. Here we create active and durable metal–oxide interfaces in porous single-crystalline (PSC) CeO₂ monoliths with in situ exsolved single-crystalline (SC) Ni particles and show efficient dry reforming of CH₄/CO₂ at temperatures as low as 450 °C. We show the excellent and durable performance with ≈20 % of CH₄ conversion and ≈30 % of CO₂ conversion even in a continuous operation of 240 hours. The well-defined active metal–oxide interfaces, created by exsolving SC Ni nanoparticles from PSC Ni_xCe_1?xO₂ to anchor them on PSC CeO₂ scaffolds, prevent nanoparticle sintering and enhance the coking resistance due to the stronger metal–support interactions. Our work would enable an industrially and economically viable path for carbon reclamation, and the technique of creating active and durable metal–oxide interfaces in PSC monoliths could lead to stable catalyst designs for many challenging reactions.     

Thermally Stable and Regenerable Platinum–Tin Clusters for Propane Dehydrogenation Prepared by Atom Trapping on Ceria

Ceria (CeO₂) supports are unique in their ability to trap ionic platinum (Pt), providing exceptional stability for isolated single atoms of Pt. The reactivity and stability of single-atom Pt species was explored for the industrially important light alkane dehydrogenation reaction. The single-atom Pt/CeO₂ catalysts are stable during propane dehydrogenation, but are not selective for propylene. DFT calculations show strong adsorption of the olefin produced, leading to further unwanted reactions. In contrast, when tin (Sn) is added to CeO₂, the single-atom Pt catalyst undergoes an activation phase where it transforms into Pt–Sn clusters under reaction conditions. Formation of small Pt–Sn clusters allows the catalyst to achieve high selectivity towards propylene because of facile desorption of the product. The CeO₂-supported Pt–Sn clusters are very stable, even during extended reaction at 680 °C. Coke formation is almost completely suppressed by adding water vapor to the feed. Furthermore, upon oxidation the Pt–Sn clusters readily revert to the atomically dispersed species on CeO₂, making Pt–Sn/CeO₂ a fully regenerable catalyst.     

CATALYST TECHNOLOGY DEVELOPMENT FROM MACRO-, MICRO- DOWN TO NANO-SCALE

Catalyst and catalytic process technology has been an ever-growing field that involves chemical engineering, chemistry, and material science. A number of excellent review articles and books have been published on the subject. In this work, the author reviews the evolution and development of catalyst products with multi-scale methodology. The catalyst technologies are classified into three levels, macro-scale （reactor size）, mini-and micro-scale （catalyst unit）, and nano-scale （catalyst intrinsic structures）. Innovation at different scales requires different sets of expertise, method, and knowledge. Specific examples of significant impact to practical application are used to illustrate technology development at each scale. The multi-scale analysis enables clear delineation of technology components and their relationship for a catalyst product and catalytic process. Manipulation of catalyst structures at nano-scale to increase intrinsic activity and/or selectivity is considered of large potential for future catalyst product development. Recent research results on Cu-CeO2 and Au-CeO2 composite catalysts for air pollution control and hydrogen production are used to show how novel catalytic properties can be discovered by unique combination of different but common materials at the nano-scale.     

固体电解质Ce_(0.9)Er_(0.1-x)Pr_xO_(1.95+δ)的微观结构及电性能

采用柠檬酸溶胶-凝胶法制备了固体电解质Ce0.9Er0.1-xPrxO1.95+δ(x=0.02~0.08),利用X射线粉末衍射(XRD)、原子力显微镜(AFM)、拉曼光谱(Raman)、X射线光电子能谱(XPS)和交流阻抗谱研究了样品的微观结构和电性能.XRD结果表明,800℃煅烧的所有样品均形成了单相立方萤石结构;Raman光谱结果表明,Ce0.9Er0.05Pr0.05O1.95+δ具有氧缺位的立方萤石结构;XPS分析表明,Ce0.9Er0.05Pr0.05O1.95+δ存在氧缺位,Pr3+离子和Pr4+离子共存;AFM观测结果表明,1300℃下烧结的样品比1400℃下烧结的样品致密;交流阻抗谱结果表明,Pr掺杂量x=0.05时,Ce0.9Er0.05Pr0.05O1.95+δ的电导率最高(σ600℃=1.34×10-2S/cm,Ea=0.90 e V),比未掺杂Pr的Ce0.9Er0.1O1.95(σ600℃=8.81×10-3S/cm,Ea=0.92 e V)提高了52%,说明在Ce0.9Er0.1O1.95中适量掺杂Pr可提高材料的电导率,降低活化能.     

Carbon to electricity in a solid oxide fuel cell combined with an internal catalytic gasification process

This study explores strategies to develop highly efficient direct carbon fuel cells (DCFCs) by com‐bining a solid‐oxide fuel cell (SOFC) with a catalyst‐aided carbon‐gasification process. This system employs Cu/CeO2 composites as both anodic electrodes and carbon additives in a cell of the type:carbon|Cu‐CeO2/YSZ/Ag|air. The study investigates the impact on in situ carbon‐gasification and DCFC performance characteristics of catalyst addition and variation in the carrier gas used (inert He versus reactive CO2). The results indicate that cell performance is significantly improved by infusing the catalyst into the carbon feedstock and by employing CO2 as the carrier gas. At 800 °C, the maxi‐mum power output is enhanced by approximately 40% and 230% for carbon/CO2 and car‐bon/catalyst/CO2 systems, respectively, compared with that of the carbon/He configuration. The increase observed when employing the catalyst and CO2 as the carrier gas can be primarily at‐tributed to the pronounced effect of the catalyst on carbon‐gasification through the re‐verse‐Boudouard reaction, and the subsequent in situ electro‐oxidation of CO at the anode three‐phase boundary.