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1.
Three types of CeO 2–ZrO 2 (Ce:Zr=1:1 molar ratio) compounds with different oxygen storage/release capacities (OSCs) were characterized by means of the Ce K-edge and Zr K-edge X-ray absorption fine structure (XAFS). In order to investigate the relationship between the OSC and local structure, the quantitative EXAFS curve-fitting analysis was applied. By enhancing the homogeneity of the Ce and Zr atoms in the CeO 2–ZrO 2 solid solution, the OSC performance increased. Especially, the atomically homogeneous Ce 0.5Zr 0.5O 2 solid solution exhibited the highest OSC among these CeO 2–ZrO 2 samples. Additionally, the local oxygen environment around Ce and Zr was remarkably modified by enhancing the homogeneity of the CeO 2–ZrO 2 solid solution. It was postulated that the enhancement of the homogeneity of the CeO 2–ZrO 2 solid solution and the modification of the oxygen environment would be the source for the OSC improvement. 相似文献
2.
The promotive effects of cerium oxide on commercial three-way catalysts (TWCs) for purification of motor exhaust gases have been widely investigated in recent years. This work shows the cooperative effects of CeO 2–Pd on the kinetics of CO oxidation over Pd/CeO 2–ZrO 2. Under reducing-to-moderately oxidizing conditions, a zero-order O 2 pressure dependence is found which can be interpreted on the basis of a mechanism involving a reaction between CO adsorbed on Pd and surface oxygen from the support. The high oxygen-exchange capability of the CeO 2–ZrO 2 support, as determined from temperature-programmed reduction/oxygen uptake measurements is suggested as being responsible for such a catalytic behavior. 相似文献
4.
以Zr(NO 3) 4·5H 2O和Na 2SiO 3·9H 2O为原料,利用共沉淀法制备前驱体,浸渍添加稀土Ce和La,一定温度焙烧后制得掺杂稀土S 2O 82-/ZrO 2-SiO 2固体超强酸。通过XRD、FT-IR和SEM对催化剂进行表征,以硬脂酸的酯化合成反应为探针,考察制备条件对催化剂性能的影响以及催化剂的重复使用率。结果表明,相对于未改性的S 2O 82-/ZrO 2-SiO 2催化剂,添加了Ce或La的固体超强酸酯化催化活性及重复使用性能均有提高。 相似文献
5.
MnO x–CeO 2 mixed oxides with a Mn/(Mn + Ce) molar ratios of 0–1 were prepared by a modified coprecipitation method and investigated for the complete oxidation of formaldehyde. The MnO x–CeO 2 with Mn/(Mn + Ce) molar ratio of 0.5 exhibited the highest catalytic activity among the MnO x–CeO 2 mixed oxides. Structure analysis by X-ray powder diffraction and temperature-programmed reduction of hydrogen revealed that the formation of MnO x–CeO 2 solid solution greatly improved the low-temperature reducibility, resulting in a higher catalytic activity for the oxidation of formaldehyde. Promoting effect of Pt on the MnO x–CeO 2 mixed oxide indicated that both the Pt precursors and the reduction temperature greatly affected the catalytic performance. Pt/MnO x–CeO 2 catalyst prepared from chlorine-free precursor showed extremely high activity and stability after pretreatment with hydrogen at 473 K. 100% conversion of formaldehyde was achieved at ambient temperature and no deactivation was observed for 120 h time-on-stream. The promoting effect of Pt was ascribed to enhance the effective activation of oxygen molecule on the MnO x–CeO 2 support. 相似文献
6.
A new proton-conductive composite of NH 4PO 3–(NH 4) 2Mn(PO 3) 4 was synthesized and characterized as a potential electrolyte for intermediate temperature fuel cells that operated around 250 °C. Thermal gravimetric analysis and X-ray diffraction investigation showed that (NH 4) 2Mn(PO 3) 4 was stable as a supporting matrix for NH 4PO 3. The composite conductivity, measured using impedance spectroscopy, improved with increasing the molar ratio of NH 4PO 3 in both dry and wet atmospheres. A conductivity of 7 mS cm −1 was obtained at 250 °C in wet hydrogen. Electromotive forces measured by hydrogen concentration cells showed that the composite was nearly a pure protonic conductor with hydrogen partial pressure in the range of 10 2–10 5 Pa. The proton transference number was determined to be 0.95 at 250 °C for 2NH 4PO 3–(NH 4) 2Mn(PO 3) 4 electrolyte. Fuel cells using 2NH 4PO 3–(NH 4) 2Mn(PO 3) 4 as an electrolyte and the Pt–C catalyst as an electrode were fabricated. Maximum power density of 16.8 mW/cm 2 was achieved at 250 °C with dry hydrogen and dry oxygen as the fuel and oxidant, respectively. However, the NH 4PO 3–(NH 4) 2Mn(PO 3) 4 electrolyte is not compatible with the Pt–C catalyst, indicating that it is critical to develop new electrode materials for the intermediate temperature fuel cells. 相似文献
7.
Rhodium (Rh) is a critical component of current automotive three-way catalysts (TWCs), particularly with regard to NO x and CO conversion at rich and stoichiometric air–fuel ratios (A/F). Rh supported on CeO 2 was active for NO x and CO conversions but could be deactivated easily by high temperature aging. The cause of the deactivation is ascribed to the sintering of CeO 2. ZrO 2 incorporation into CeO 2 is reported to have high thermal durability in terms of oxygen storage capacity (OSC). There has been no report showing direct experimental evidence that Rh-loaded on CeO 2–ZrO 2 mixed oxides induced effects on TWC performance improvement in the actual automotive exhaust. In the present paper, the Rh-CeO 2 interaction contributing to NO x reduction and the catalytic behavior of Rh-loaded CeO 2–ZrO 2 mixed oxide is addressed. Incorporating CeO 2–ZrO 2 into a catalyst offered significant improvement in light-off and warmed-up performances in model gas test. Newly designed TWC including the Rh/CeO 2–ZrO 2 component were aged and evaluated on an engine dynamometer. Result of engine dynamometer evaluation also revealed that significant improvement in the thermal durability can be achieved by the utilization of the optimized Rh-loaded CeO 2–ZrO 2 mixed oxide. 相似文献
8.
A systematic reactivity study of N 2O, NO, and NO 2 on highly dispersed CuO phases over modified silica supports (SiO 2–Al 2O 3, SiO 2–TiO 2, and SiO 2–ZrO 2) has been performed. Different reaction paths for the nitrogen oxide species abatement were studied: from direct decomposition (N 2O) to selective reductions by hydrocarbons (N 2O, NO, and NO 2) and oxidation (NO to NO 2). The oxygen concentration, temperature, and contact time, were varied within suitable ranges in order to investigate the activity and in particular the selectivity in the different reactions studied. The support deeply influenced the catalytic properties of the active copper phase. The most acidic supports, SiO 2–Al 2O 3 and SiO 2–ZrO 2, led to a better activity and selectivity of CuO for the reactions of N 2O, NO, and NO 2 reductions and N 2O decomposition than SiO 2–TiO 2. The catalytic results are discussed in terms of actual turnover frequencies starting from the knowledge of the copper dispersion values. 相似文献
9.
The introduction of trivalent cation — Y 3+ or La 3+ — into the lattice of CeO 2–ZrO 2 solid solutions allows to stabilise a cubic structure at low ceria content (30 mol%). The reducibility of the samples has been compared in the experiments of temperature-programmed reduction (TPR). The introduction of lanthanum cations decreases the amount of hydrogen consumed during TPR, while the introduction of yttrium ones increases this value. At the same time, the value of temperature of the maximum speed of reduction ( Tmax) is independent on the trivalent dopant. The reducibility of these solid solutions did not change during repeated red–ox treatments at temperature below 1220 K. It is connected with the high thermostability of all systems in this temperature interval. TPR up to 1470 K causes a significant shift of Tmax value to higher temperature and a slight decrease of hydrogen consumption in two to three cycles. It is suggested that this alterations are connected with the sharp decrease of the specific surface area of all samples and partially phase decomposition of CeO 2–ZrO 2 and Y 2O 3–CeO 2–ZrO 2 solid solutions. Raman characterisation of the oxygen sublattice of the fresh samples and of the samples after TPR has been carried out. 相似文献
10.
The catalytic activity study of cobalt oxides dispersed on different supports evidenced first the highest performances of zirconia based catalysts in the reaction of toluene oxidation. The influence of the presence of ethylenediamine (en) during the preparation of Co/ZrO 2 and the ZrO 2 support modification by Y 2O 3 were then studied and compared with reference catalyst prepared conventionally by impregnation of ZrO 2 with an aqueous solution of Co(NO 3) 2. Addition of an aqueous solution of ethylenediamine to a cobalt nitrate solution led to a strong increase on the catalytic activity of the activated solids in the toluene deep oxidation as compared with the reference catalyst. The best catalytic results were explained in terms of cobalt oxides dispersion but also in terms of Co–support interaction. The generated cobalt species were reducible at much lower temperatures and then were more active in the toluene total oxidation. Finally an efficient catalyst for VOC oxidation was produced combining the modifications of ZrO 2 by yttrium and of the precursor. 相似文献
11.
A series of cobalt–cerium mixed oxide catalysts (Co 3O 4–CeO 2) with a Ce/Co molar ratio of 0.05 were prepared by co-precipitation (with K 2CO 3 and KOH as the respective precipitant), impregnation, citrate, and direct evaporation methods and then tested for the catalytic decomposition of N 2O. XRD, BET, XPS, O 2-TPD and H 2-TPR methods were used to characterize the catalysts. Catalysts with a trace amount of residual K exhibited higher catalytic activities than those without. The presence of appropriate amount of K in Co 3O 4–CeO 2 may improve the redox property of Co 3O 4, which is important for the decomposition of N 2O. When the amount of K was constant, the surface area became the most important factor for the reaction. The co-precipitation-prepared catalyst with K 2CO 3 as precipitant exhibited the best catalytic performance because of the presence of ca. 2 mol% residual K and the high surface area. We also discussed the rate-determining step of the N 2O decomposition reaction over these Co 3O 4–CeO 2 catalysts. 相似文献
12.
The influence of catalyst pre-treatment temperature (650 and 750 °C) and oxygen concentration ( λ = 8 and 1) on the light-off temperature of methane combustion has been investigated over two composite oxides, Co 3O 4/CeO 2 and Co 3O 4/CeO 2–ZrO 2 containing 30 wt.% of Co 3O 4. The catalytic materials prepared by the co-precipitation method were calcined at 650 °C for 5 h (fresh samples); a portion of them was further treated at 750 °C for 7 h, in a furnace in static air (aged samples). Tests of methane combustion were carried out on fresh and aged catalysts at two different WHSV values (12 000 and 60 000 mL g−1 h−1). The catalytic performance of Co3O4/CeO2 and Co3O4/CeO2–ZrO2 were compared with those of two pure Co3O4 oxides, a sample obtained by the precipitation method and a commercial reference. Characterization studies by X-ray diffraction (XRD), BET and temperature-programmed reduction (TPR) show that the catalytic activity is related to the dispersion of crystalline phases, Co3O4/CeO2 and Co3O4/CeO2–ZrO2 as well as to their reducibility. Particular attention was paid to the thermal stability of the Co3O4 phase in the temperature range of 750–800 °C, in both static (in a furnace) and dynamic conditions (continuous flow). The results indicate that the thermal stability of the phase Co3O4 heated up to 800 °C depends on the size of the cobalt oxide crystallites (fresh or aged samples) and on the oxygen content (excess λ = 8, stoichiometric λ = 1) in the reaction mixture. A stabilizing effect due to the presence of ceria or ceria–zirconia against Co3O4 decomposition into CoO was observed. Moreover, the role of ceria and ceria–zirconia is to maintain a good combustion activity of the cobalt composite oxides by dispersing the active phase Co3O4 and by promoting the reduction at low temperature. 相似文献
13.
The NiSO 4 supported on Fe 2O 3-promoted ZrO 2 catalysts were prepared by the impregnation method. Fe 2O 3-promoted ZrO 2 was prepared by the coprecipitation method using a mixed aqueous solution of zirconium oxychloride and iron nitrate solution followed by adding an aqueous ammonia solution. No diffraction line of nickel sulfate was observed up to 20 wt.%, indicating good dispersion of nickel sulfate on the surface of Fe 2O 3–ZrO 2. The addition of nickel sulfate (or Fe 2O 3) to ZrO 2 shifted the phase transition of ZrO 2 (from amorphous to tetragonal) to higher temperatures because of the interaction between nickel sulfate (or Fe 2O 3) and ZrO 2. 15-NiSO 4/5-Fe 2O 3–ZrO 2 containing 15 wt.% NiSO 4 and 5 mol% Fe 2O 3, and calcined at 500 °C exhibited a maximum catalytic activity for ethylene dimerization. NiSO 4/Fe 2O 3–ZrO 2 catalysts was very effective for ethylene dimerization even at room temperature, but Fe 2O 3–ZrO 2 without NiSO 4 did not exhibit any catalytic activity at all. The catalytic activities were correlated with the acidity of catalysts measured by the ammonia chemisorption method. The addition of Fe 2O 3 up to 5 mol% enhanced the acidity, surface area, thermal property, and catalytic activities of catalysts gradually, due to the interaction between Fe 2O 3 and ZrO 2 and due to consequent formation of Fe–O–Zr bond. 相似文献
14.
We present a systematic study of the NH 3-SCR reactivity over a commercial V 2O 5–WO 3/TiO 2 catalyst in a wide range of temperatures and NO/NO 2 feed ratios, which cover (and exceed) those of interest for industrial applications to the aftertreatment of exhaust gases from diesel vehicles. The experiments confirm that the best deNO x efficiency is achieved with a 1/1 NO/NO 2 feed ratio. The main reactions prevailing at the different operating conditions have been identified, and an overall reaction scheme is herein proposed. Particular attention has been paid to the role of ammonium nitrate, which forms rapidly at low temperatures and with excess NO2, determining a lower N2 selectivity of the deNOx process. Data are presented which show that the chemistry of the NO/NO2–NH3 reacting system can be fully interpreted according to a mechanism which involves: (i) dimerization/disproportion of NO2 and reaction with NH3 and water to give ammonium nitrite and ammonium nitrate; (ii) reduction of ammonium nitrate by NO to ammonium nitrite; (iii) decomposition of ammonium nitrite to nitrogen. Such a scheme explains the peculiar deNOx reactivity at low temperature in the presence of NO2, the optimal stoichiometry (NO/NO2 = 1/1), and the observed selectivities to all the major N-containing products (N2, NH4NO3, HNO3, N2O). It also provides the basis for the development of a mechanistic kinetic model of the NO/NO2–NH3 SCR reacting system. 相似文献
15.
SnO 2–ZrO 2 nanocomposite catalysts with different compositions ranging from 0 to 100% of SnO 2 were prepared at room temperature by co-precipitation method using aqueous ammonia as a hydrolyzing agent. X-ray diffraction, transmission electron microscopic characterization revealed the SnO 2–ZrO 2 nanocomposite behavior. Acid–base properties of these catalysts were ascertained by temperature-programmed desorption (TPD) of NH 3 and CO 2. Both acidic and basic sites distribution of the nanocomposite catalysts is quite different from those of respective single oxides (SnO 2 or ZrO 2). Catalytic activity of these nanocomposite catalysts for ethylbenzene dehydrogenation (EBD) to styrene in the presence of excess CO 2 was evaluated. The change in the acid–base bi-functionality of the nanocomposite catalysts in comparison with single oxides had profound positive influence in enhancing the catalytic activity. 相似文献
16.
The direct decomposition of nitric oxide (NO) over barium catalysts supported on various metal oxides was examined in the absence and presence of O 2. Among the Ba catalysts supported on single-component metal oxides, Ba/Co 3O 4 and Ba/CeO 2 showed high NO decomposition activities, while Ba/Al 2O 3, Ba/SiO 2, and Ba/TiO 2 exhibited quite low activities. The effect of an addition of second components to Co and Ce oxides was further examined, and it was found that the activities were significantly enhanced using Ce–Mn mixed oxides as support materials. XRD results indicated the formation of CeO 2–MnO x solid solutions with the cubic fluorite structure. O 2-TPD of the CeO 2–MnO x solid solutions showed a large desorption peak in a range of relatively low temperature. The BET surface areas of the CeO 2–MnO x solid solutions were larger than those of pure CeO 2 and Mn 2O 3. These effects caused by the addition of Mn are responsible for the enhanced activities of the Ba catalysts supported on Ce–Mn mixed oxides. 相似文献
17.
Manganese–cerium mixed oxide catalysts with different molar ratio Mn/(Mn + Ce) (0, 0.25, 0.50, 0.75, 1) were prepared by citric acid method and investigated concerning their adsorption behavior, redox properties and behavior in the selective catalytic reduction of NO x by NH 3. The studies based on pulse thermal analysis combined with mass spectroscopy and FT-IR spectroscopy uncovered a clear correlation between the dependence of these properties and the mixed oxide composition. Highest activity to nitrogen formation was found for catalysts with a molar ratio Mn/(Mn + Ce) of 0.25, whereas the activity was much lower for the pure constituent oxides. Measurements of adsorption uptake of reactants, NO x (NO, NO 2) and NH 3, and reducibility showed similar dependence on the mixed oxide composition indicating a clear correlation of these properties with catalytic activity. The adsorption studies indicated that NO x and NH 3 are adsorbed on separate sites. Consecutive adsorption measurements of the reactants showed similar uptakes as separate measurements indicating that there was no interference between adsorbed reactants. Mechanistic investigations by changing the sequence of admittance of reactants (NO x, NH 3) indicated that at 100–150 °C nitrogen formation follows an Eley–Rideal type mechanism, where adsorbed ammonia reacts with NO x in the gas phase, whereas adsorbed NO x showed no significant reactivity under conditions used. 相似文献
18.
MnO x–CeO 2 mixed oxides prepared by sol–gel method, coprecipitation method and modified coprecipitation method were investigated for the complete oxidation of formaldehyde. Structure analysis by H 2-TPR and XPS revealed that there were more Mn 4+ species and richer lattice oxygen on the surface of the catalyst prepared by the modified coprecipitation method than those of the catalysts prepared by sol–gel and coprecipitation methods, resulting in much higher catalytic activity toward complete oxidation of formaldehyde. The effect of calcination temperature on the structural features and catalytic behavior of the MnO x–CeO 2 mixed oxides prepared by the modified coprecipitation was further examined, and the catalyst calcined at 773 K showed 100% formaldehyde conversion at a temperature as low as 373 K. For the samples calcined below 773 K, no any diffraction peak corresponding to manganese oxides could be detected by XRD measurement due to the formation of MnO x–CeO 2 solid solution. While the diffraction peaks corresponding to MnO 2 phase in the samples calcined above 773 K were clearly observed, indicating the occurrence of phase segregation between MnO 2 and CeO 2. Accordingly, it was supposed that the strong interaction between MnO x and CeO 2, which depends on the preparation route and the calcination temperature, played a crucial role in determining the catalytic activity toward the complete oxidation of formaldehyde. 相似文献
19.
High surface area CeO 2–ZrO 2 mixed oxides were treated at 900–950°C either under wet air or under successive reducing and oxidizing atmospheres in order to study the evolution of the oxygen storage capacity (OSC) of these solids after different aging treatments. Several complementary methods were used to characterize the redox behavior: temperature programmed reduction (TPR) by H 2, TPO, magnetic susceptibility measurements to obtain the Ce 3+ content, FT-IR spectroscopy of adsorbed methanol and a method to compare the oxygen buffering capacity (OBC) of the oxides. All the results confirm that the mixed oxides exhibit better redox properties than pure ceria, particularly after aging. The enhancement in the OSC at moderate temperature has to be related to a deeper penetration of the reduction process from the surface into the under-layers. Redox cycling aging promotes the reduction at low temperature of all the mixed oxides, the improvement being much more important for low surface area aged samples. The magnitude of this effect does not depend on the BET surface areas which have similar values after cycling. This underlines the critical influence that the preparation and activation procedure have on the final OSC behaviors of the ceria–zirconia mixed oxides. 相似文献
20.
以硝酸铈[Ce(NO 3) 3]为原料,碳酸氢铵(NH 4HCO 3)为沉淀剂,弱阳离子表面活性剂聚乙烯吡咯烷酮(PVP)为软模板剂,通过控制初始PVP浓度、加料反应时间、陈化时间制备得到颗粒均匀、类似花状结构的碳酸铈[Ce 2(CO 3) 3]粒子。采用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、傅里叶红外光谱仪(FTIR)对制得的碳酸铈样品进行分析表征。结果表明,制备颗粒均匀、形状规则的花状碳酸铈粒子的最佳条件为:初始PVP浓度为2g/L,加料反应时间为1h,搅拌速度为300r/min,陈化时间为4h。并对PVP调控合成特殊形貌碳酸铈的调控机理进行了初步探究:PVP 通过酮基中的O吸附在碳酸铈晶体表面,阻碍了(002)和(040)晶面的生长,限制了晶体晶面的生长速度,从而调控碳酸铈的形貌。XRD结果表明最终产物为八水合碳酸铈。 相似文献
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