以氨水为沉淀剂反应条件对储氧材料性能的影响

以氨水为沉淀剂制备一系列储氧材料,表征了其物相组成,同时对其储氧性能和比表面积进行了测定,探讨了反应条件对储氧材料性能的影响.结果表明,前驱体到最终CeO2-ZrO2固溶体的形成是属于同晶相转化;pH值、陈化温度、反应物浓度对材料的储氧性能、比表面积、抗老化性能有着不同程度的影响.     

CeO_2-ZrO_2-La_2O_3-Pr_2O_3储氧材料制备及其负载单Pd三效催化剂性能

采用共沉淀法制备了质量分数4%La2O3和质量分数6%Pr2O3共改性的不同Ce与Zr质量比(分别为2∶7、4∶5和8∶1)的Ce O2-Zr O2-La2O3-Pr2O3储氧材料,利用BET、XRD、H2-TPR和OSC等对其织构、结构性能和氧化还原性能进行表征,并对负载Pd的三效催化剂进行模拟汽车尾气活性测试。BET结果表明,新鲜储氧材料的比表面积随着Ce含量增加逐渐增大,Ce与Zr质量比8∶1的储氧材料C8Z1具有最大比表面积109.6 m2·g-1;1 000℃空气气氛处理4 h的老化储氧材料的比表面积变化趋势与新鲜储氧材料相反,随着Ce含量增加,比表面积逐渐降低,Ce与Zr质量比为2∶7的C2Z7a具有最大比表面积55.1 m2·g-1;XRD结果表明,高Ce含量材料的抗高温结构稳定性较中低Ce含量的材料差;H2-TPR和储氧量测试表明,老化前后Ce与Zr质量比4∶5的储氧材料C4Z5均具有最佳的还原能力和最大储氧量;模拟汽车尾气测试表明,高Ce含量的Pd/C8Z1三效催化剂对CO、NO和HC具有最低的起燃温度,50%起燃温度(T50)分别为238.8℃、265.9℃和268.4℃。     

高性能铈锆钇储氧材料的制备及应用研究

以溴化十六烷基三甲基铵(CTAB)为模板剂,采用并流法与正加法制备了铈锆钇稀土储氧材料.结果表明:并流法制备的样品具有高比表面积和储氧性能,经600 ℃焙烧后,其比表面积高达172.4 m2/g,储氧量为637.5 μmol/g;高温老化处理后,储氧量仍高达590 μmol/g,明显优于正加法制备的样品,表现出良好的抗老化能力和储氧性能.活性评价结果表明,含铈锆钇储氧材料的三效催化剂均能满足压缩天然气汽车和液化石油气汽车的排放要求,其中,液化石油气汽车的排放效果更佳.     

超声对纳米稀土复合氧化物性能的影响

采用溶胶-凝胶法,通过控制超声时间制备系列纳米稀土复合氧化物,使用TEM、BET和TPR-H₂技术对其进行了表征。结果表明,纳米复合氧化物颗粒以不规则球形粒子存在,比表面积较小,储氧值位于（867.4～1 051.1） mmol·g^－1,还原起始点温度为（130～150） ℃,超声时间越长,得到的复合氧化物颗粒的性能越佳。纳米稀土复合氧化物优越的起燃和储氧特性使其有望成为新型的三效催化剂涂层材料。     

掺杂方式对纳米（Ce-Zr-Pr）O2/γ-Al2O3陶瓷载体涂层性能的影响

采用在拟薄水铝石溶胶中分别掺杂纳米(Ce-Zr-Pr)O2固溶体粉末和前驱体溶胶的方式,制备(Ce-Zr-Pr)O2/γ-Al2O3蜂窝陶瓷载体涂层。并利用XRD、H2-TPR、BET和氧脉冲等手段研究掺杂方式对涂层的晶相结构、还原性能、比表面积和储氧性能的影响,由SEM照片观察涂层的表面形貌。结果表明,两种掺杂方式制备(Ce-Zr-Pr)O2/γ-Al2O3涂层均具有较好的织构和储氧性能。其中前驱体溶胶掺杂方式制备涂层液的粒径小,分布范围窄,且涂层表面光滑均匀,比表面积和储氧性能较高。(Ce-Zr-Pr)O2/γ-Al2O3蜂窝陶瓷载体涂层负载的单Pd三效催化剂具有低的起燃温度和优异的三效催化转化活性。     

高储氧能力的Ce-Zr-La-Y-Al储氧材料的制备

采用共沉淀法制备了多组分储氧材料Ce0.5Zr0.15Y0.075La0.075Al0.2O1.825。在以氨水和碳酸铵为共沉淀剂、聚乙二醇为表面活性剂、pH值约10.0、H2O2与Ce的摩尔比为1∶1、聚乙二醇与氧化物的质量比为1∶1、陈化温度为90℃的条件下,500℃煅烧时储氧材料的储氧量达587.0μmol.g-1,1000℃煅烧时储氧量达399.9μmol.g-1。老化样品的储氧量远高于摩托车欧Ⅲ排放标准中对三效催化剂中储氧材料储氧性能的要求,且该储氧材料的储/放氧性能稳定。     

新型储氧材料Ce0.6Tb0.1Zr0.3O2在三效催化剂中的应用研究

采用共沉淀技术制备出了Ce0.6Tb0.1Zr0.3O2固溶体,并对其进行了比表面积测试和XRD表征.将其用于全钯三效催化剂的制备,对三效催化剂的性能进行了评价.结果表明Ce0.6Tb0.1Zr0.3O2和Ce0.6Zr0.4O2的结构相似,物相均一性好,稳定性高,且具有较大的比表面积.含Ce0.6Tb0.1Zr0.3O2的三效催化剂具有较高的催化活性和较宽的空燃比窗口,HC、CO和NO的起燃温度分别为177℃、173℃和176℃,适于作为新一代三效催化剂的储氧材料.     

高储氧能力的Ce—Zr—La—Y—AI储氧材料的制备

采用共沉淀法制备了多组分储氧材料ce0.5 Zr0.15 Y0.075 La0.075 O1.825。在以氨水和碳酸铵为共沉淀剂、聚乙二醇为表面活性剂、pH值约10．O、H202与Ce的摩尔比为1：1、聚乙二醇与氧化物的质量比为1：1、陈化温度为90℃的条件下,500℃煅烧时储氧材料的储氧量达587．0μmo1．g-1,1000℃煅烧时储氧量达399．9μmol·g-1。老化样品的储氧量远高于摩托车欧Ⅲ排放标准中对三效催化剂中储氧材料储氧性能的要求,且该储氧材料的储／放氧性能稳定。     

三效催化剂用储氧材料的研究进展

论述了国内外储氧材料的研究进展,简述了不同种类的储氧材料。对固溶体储氧材料CeO2的改性研究表明,过渡金属元素或稀土金属元素被嵌入CeO2晶格形成固溶体,可极大地改善CeO2基储氧材料的储氧性能和热稳定性能,促进CeO2基储氧材料广泛的实际应用。     

YBaCo_4O_(7+δ)的制备及其氧吸附/脱附性能研究

采用溶胶凝胶法和固态反应法制备了不同比表面积的YBaCo_4O_(7+δ)氧吸附材料,采用X射线衍射仪、电子扫描显微镜对不同比表面积粒径的YBaCo_4O_(7+δ)材料的结构、形貌进行了表征,测试结果表明:溶胶凝胶法和固态反应法制备的YBaCo_4O_(7+δ)材料均为六方密排晶体结构(空间群为P63mc(186)),与固态反应法相比,溶胶凝胶法制备的YBaCo_4O_(7+δ)氧吸附材料粒径较小,且分布较为集中,并研究了粒径对YBaCo_4O_(7+δ)材料氧吸附/脱附性能的影响,从室温到1000℃,不同粒径的YBaCo_4O_(7+δ)氧吸附材料均经历两次氧吸附过程,而溶胶凝胶法制备的YBaCo_4O_(7+δ)材料氧吸附性能明显高于固态反应法制备的YBaCo_4O_(7+δ)材料的氧吸附性能,这是因为溶胶凝胶法制备的YBaCo_4O_(7+δ)材料具有较小的尺寸,较大的比表面积的缘故。     

Characterization of the dynamic oxygen migration over Pt/CeO2-ZrO2 catalysts by O/O isotopic exchange reaction

To characterize the oxygen mobility over metal supported catalysts on a dynamic and in situ base, ¹⁸O/¹⁶O isotopic exchange reaction combined with CO oxidation was designed and exemplified on three kinds of three way catalysts of Pt/CeO₂-ZrO₂ (CZ-O, CZ-D and CZ-R). The obtained oxygen diffusion coefficients, oxygen release rate, and oxygen storage capacity were discussed and correlated with XRD spectra and other physical parameters. It was found that the oxygen mobility and oxygen storage capacity were parallel to the structural homogeneity of Zr introduction into the CeO₂ frame work, and decreased as: CZ-R > CZ-D > CZ-O. These results indicated that this combined isotopic exchange technique could be used to quantify the surface and bulk oxygen mobility, the oxygen storage capacity and oxygen release rate over the metal supported catalysts, and could be employed as a meaningful probe into the nature of CeO₂-ZrO₂ oxygen storage material. The oxygen mobility is also another important indicator for the development of oxygen storage materials.     

High-throughput approach to the catalytic combustion of diesel soot II: Screening of oxide-based catalysts

Following the development of a high-throughput (HT) methodology for the evaluation of diesel soot oxidation catalysts in a 16 parallel channels reactor, a library of over 60 catalysts was tested under optimized conditions. The catalyst compositions were chosen to include solids which specific properties like oxygen storage capacity, oxygen mobility and ionic conductivity. The key parameters for high activity appear related to the presence of active and mobile surface oxygen species, and to an appropriate catalyst particle size in order to favour the number of contacts with the soot. In contrast, high oxygen storage capacity and bulk oxygen ion mobility do not appear as relevant properties for high catalytic activity. Nine new formulations were found to perform better than the reference catalyst “high surface area (HSA) ceria” (Rhodia).     

Effect of Thermal Aging on the Transient Kinetics of Oxygen Storage and Release of Commercial Ce x Zr1−x O2-based Solids

The use of powerful analytical methodologies for the evaluation of the performance of commercial oxygen storage materials based on oxygen transient isothermal isotopic exchange experiments is illustrated in this study. Ce _x Zr_1?x O₂-based oxygen storage materials were investigated. The materials were characterized for their dynamic oxygen storage and release properties through the pulse injection technique allowing the measurement of the oxygen storage capacity (OSC), and for their surface and bulk oxygen mobility through transient isothermal ¹⁸O isotopic exchange experiments. Very high OSC values were obtained after calcination in air at T_calc. = 700 or 850 °C. However, after thermal aging at 1000 or 1100 °C of the as prepared samples, a significant deterioration of their OSC was observed. This fact was found to correlate with the significant increase in the activation energy of surface oxygen mobility. On the contrary, smaller increase in the activation energy of bulk oxygen diffusion with increasing T_calc. was observed.     

Role of Surface Area in Oxygen Storage Capacity of Ceria–Zirconia as Soot Combustion Catalyst

Two thermal stable phases, Ce_0.75Zr_0.25O₂ and Ce_0.16Zr_0.84O₂, with different surface area were prepared by coprecipitation. The oxygen storage capacity (OSC) measurements were carried out at 500 °C under both transient (CO–O₂ cycle at 0.05, 0.1 and 0.25 Hz) and stationary reaction conditions (CO pulse). In the oxygen storage/release process, the rate-determine step is surface reactions when the specific surface area is lower than 60 m²/g. When the surface area increases further, the influence of surface area is less important. The increased surface area favors diesel soot catalytic combustion via providing more redox sites to activate adsorbed oxygen. Nevertheless, this effect is less important when the specific surface area is larger than 40 m²/g, especially under loose contact condition.     

Hydrothermal Aging-Induced Changes in Washcoats of Commercial Three-Way Catalysts

In order to quantify hydrothermal aging effects on the mono- and bi-metallic Pd and Rh supported on cerium-zirconium promoted alumina commercial three-way catalysts (TWCs), the catalysts were tested both fresh and after accelerated hydrothermal aging. The catalytic tests showed clear deactivation of the aged samples and influence on TWC’s property, such as: light-off temperature, specific surface area (BET), dispersion of noble metals, oxygen storage capacity, oxygen storage capacity complete and labile oxygen storage capacity. Water inhibition have been investigated and confirmed for the performance of NO_x reduction of the fresh catalyst. X-ray photoelectron spectroscopy was used to study changes in the oxidation state of the Pd and Rh present in the washcoat of the catalyst, before and after hydrothermal aging. Element maps by SEM-EDX analysis was perform in order to characterize the catalysts morphology, the surface’s composition and element distribution.     

Hydrogen adsorption in different carbon nanostructures

Hydrogen adsorption in different carbonaceous materials with optimized structure was investigated at room temperature and 77 K. Activated carbon, amorphous carbon nanotubes, SWCNTs and porous carbon samples all show the same adsorption properties. The fast kinetics and complete reversibility of the process indicate that the interaction between hydrogen molecules and the carbon nanostructure is due to physisorption. At 77 K the adsorption isotherm of all samples can be explained with the Langmuir model, while at room temperature the storage capacity is a linear function of the pressure. The surface area and pore size of the carbon materials were characterized by N₂ adsorption at 77 K and correlated to their hydrogen storage capacity. A linear relation between hydrogen uptake and specific surface area (SSA) is obtained for all samples independent of the nature of the carbon material. The best material with a SSA of 2560 m²/g shows a storage capacity of 4.5 wt% at 77 K.     

Preparation of Isolated Single-walled Carbon Nanotubes with High Hydrogen Storage Capacity

Isolated single-walled carbon nanotubes with high proportion of opening tips were synthesized by using alcohol as carbon source. The mechanism of cutting action of oxygen was proposed to explain its growth. Compared with carbon nanotubes synthesized with benzene as carbon source, their specific surface area was heightened by approximately 2.2 times (from 200.5 to 648 m2/g) and the hydrogen storage capacity was increased by approximately 6.5 times (from 0.95 to 7.17%, w) which had exceeded DOE energy standard of vehicular hydrogen storage.     

蜂窝陶瓷蓄热材料的研究现状

蜂窝陶瓷蓄热材料应该具有热膨胀系数低、比热容大、比表面积大、导热性能好、抗热震性好等特性。本文详细介绍了几种多孔陶瓷材料的优缺点,指出堇青石质复相材料是目前研究最广泛的蜂窝陶瓷材料。堇青石与多种催化剂匹配性好,比表面积大、热膨胀系数小,但耐热性稍差,于是通过添加一些添加剂来提高堇青石作为蜂窝陶瓷蓄热体的性能。这些添加剂与堇青石结合形成复相材料,可以降低热膨胀系数、提高抗热震性等。     

纳米粒子对熔盐复合蓄热材料热物性的影响

为了得到SiO₂纳米粒子含量对SiO₂/NaNO₃-KNO₃/EG复合蓄热材料比热容和热导率的影响，通过机械分散法，采用NaNO₃-KNO₃和不同质量分数（0.1%，0.5%，1%，2%，3%）的SiO₂纳米粒子所形成的熔盐纳米材料作为蓄热材料，膨胀石墨（EG）作为基体材料，制备出纳米SiO₂/NaNO₃-KNO₃/EG复合材料。对复合材料的比热容和热导率进行了测量，同时用扫描电镜对其微观结构特征进行了分析。结果表明，SiO₂纳米粒子的质量分数为1%时，复合材料的平均比热容和热导率分别为3.92 J/(g·K)和8.47 W/(m·K)，与其他纳米SiO₂添加比例相比，其比热容和热导率分别提高了1.37～2.17倍和1.7～3.2倍。这是由于复合材料表面会形成高密度的网状结构，这种具有较大比表面积和高表面能的特殊纳米结构可以提高复合材料的比热容和热导率。