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1.
Pt-Rh/CexZr1−xO2-Al2O3 with 0.6 and 1.0 wt.% noble metal loadings were prepared and characterized for their metal dispersion with respect to CexZr1−xO2-free Pt-Rh/Al2O3 in fresh, thermally aged and oxychlorinated states. Thermal ageing at 973 K led to loss of metal dispersion in all cases but to negligible effect on the dispersion of the CexZr1−xO2 component where present. Oxychlorination was able to fully recover metal dispersion in all cases but led to different effects on the redox properties of CexZr1−xO2 which appeared to be related to the metal loadings. Despite showing improved dispersion following regeneration, higher loaded catalyst showed no improvement in light-off performance for either NO reduction or CO oxidation and showed poorer oxygen storage (OSC) ability, particularly at higher temperatures. Lower loaded catalyst showed improved dispersion, improved OSC and reduced light-off temperatures for NO reduction and CO oxidation after oxychlorination compared to that in the thermally aged state.  相似文献   

2.
A series of the Ce1−xCuxO2−x/Al2O3/FeCrAl catalysts (x = 0–1) were prepared. The structure of the catalysts was characterized using XRD, SEM and H2-TPR. The catalytic activity of the catalysts for the combustion of methane was evaluated. The results indicated that in the Ce1−xCuxO2−x/Al2O3/FeCrAl catalysts the surface phase structure were the Ce1−xCuxO2−x solid solution, -Al2O3 and γ-Al2O3. The surface particle shape and size were different with the variety of the molar ratio of Ce to Cu in the Ce1−xCuxO2−x solid solution. The Cu component of the Ce1−xCuxO2−x/Al2O3/FeCrAl catalysts played an important role to the catalytic activity for the methane combustion. There were the stronger interaction among the Ce1−xCuxO2−x solid solution and the Al2O3 washcoats and the FeCrAl support.  相似文献   

3.
This study focuses on the direct sulfur recovery process (DSRP), in which SO2 can be directly converted into elemental sulfur using a variety of reducing agents over Ce1−xZrxO2 catalysts. Ce1−xZrxO2 catalysts (where x = 0.2, 0.5, and 0.8) were prepared by a citric complexation method. The experimental conditions used for SO2 reduction were as follow: the space velocity (GHSV) was 30,000 ml/g-cat h and the ratio of [CO (or H2, H2 + CO)]/[SO2] was 2.0. It was found that the catalyst and reducing agent providing the best performance were the Ce0.5Zr0.5O2 catalyst and CO, respectively. In this case, the SO2 conversion was about 92% and the sulfur yield was about 90% at 550 °C. Also, a higher efficiency of SO2 removal and elemental sulfur recovery was achieved in the reduction of SO2 with CO as a reducing agent than that with H2. In the reduction of SO2 by H2 over the Ce0.5Zr0.5O2 catalyst, SO2 conversion and sulfur yield were about 92.7% and 73%, respectively, at 800 °C. Also, the reduction of SO2 using synthetic gas with various [CO]/[H2] molar ratios over the Ce0.5Zr0.5O2 catalyst was performed, in order to investigate the possibility of using coal-derived gas as a reducing agent in the DSRP. It was found that the reactivity of the SO2 reduction using the synthetic gas with various [CO]/[H2] molar ratios was increased with increasing CO content of the synthetic gas. Therefore, it was found that the Ce1−xZrxO2 catalysts are applicable to the DSRP using coal-derived gas, which contains a larger percentage of CO than H2.  相似文献   

4.
La1−xSrxMnO3 (x=0, 0.1, 0.3, 0.5, 0.7) perovskite-type oxides (PTOs) were prepared by coprecipitation under various calcination temperature, and their performances for the NO reduction were evaluated under a simulated exhaust gas mixture. The X-ray diffraction (XRD) and thermogravimetric analysis were carried out to find the formation process of the perovskite. The NO reduction rate under different reaction temperature, the concentration of oxygen and the presence of hydrocarbon were observed by the input/output analysis. In the presence of 10% excess oxygen, the catalyst La0.7Sr0.3MnO3 calcined at 900 °C showed a NO reduction rate of 61% at 380 °C. The study of the reaction curves showed that C3H8 could act as the reducer for the NO reduction below 400 °C. The NO reduction is highly affected by increasing the O2 concentration from 0.5 to 10%, especially at high temperatures when oxygen becomes more competitive than NO on the oxidation of C3H8, leading to a decrease of the NO reduction from 100% to zero at 560 °C.  相似文献   

5.
Structural (XRD) and spectroscopic (EPR, IR and Raman) investigations were performed to elucidate the influence of CeO2 content on the phase composition and surface chemistry of CexZr1−xO2 solid solutions (x = 0.10–0.85), interacting with NO and NO2 in the absence and presence of oxygen. Strong influence of ceria loading on the adsorption modes of both nitrogen oxides and the nature of the resultant surface species was revealed. Adsorption of NO led to formation of mononitrosyl complexes, dimers and N2O, whereas interaction of NO2 with the ceria–zirconia catalyst resulted in the adsorbate disproportionation or coupling, depending on the sample composition.  相似文献   

6.
One series of LaCo1−xCuxO3 perovskites with high specific surface area was prepared by the new method designated as reactive grinding. These solids were characterized by N2 adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), H2-temperature programmed reduction (TPR), O2-temperature programmed desorption (TPD), NO + O2-TPD, C3H6-TPD, NO + O2-temperature programmed surface reaction (TPSR) under C3H6/He flow as well as catalytic reduction of NO activity tests. The catalytic performance of unsubstituted sample is poor with a maximum conversion to N2 of 19% at 500 °C at a space velocity of 55,000 h−1 (3000 ppm NO, 3000 ppm C3H6, 1% O2 in helium) but it is improved by incorporation of Cu into the lattice. A maximal N2 yield of 46% was observed over LaCo0.8Cu0.2O3 under the same conditions. Not only the abundance of -oxygen but also the mobility of β-oxygen of lanthanum cobaltite was remarkably enhanced by Cu substitution according to O2-TPD and H2-TPR studies. The better performance of Cu-substituted samples is likely to correspond to the essential nature of Cu and facility to form nitrate species in NO transformation conditions. In the absence of O2, the reduction of NO by C3H6 was performed over LaCo0.8Cu0.2O3, leading to a maximal conversion to N2 of 73% accompanied with the appearance of some organo nitrogen compounds (identified as mainly C3H7NO2). Subsequently, a mechanism involving the formation of an organic nitro intermediate, which further converts into N2, CO2 and H2O via isocyanate, was proposed. Gaseous oxygen acts rather as an inhibitor in the reaction of NO and C3H6 over highly oxidative LaCo0.8Cu0.2O3 due to the heavily unselective combustion of C3H6 by O2.  相似文献   

7.
A series of La(Co, Mn, Fe)1−x(Cu, Pd)xO3 perovskites having high specific surface areas and nanosized crystal domains was prepared by reactive grinding. The solids were characterized by N2 adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature programmed desorption (TPD) of O2, NO + O2, C3H6, in the absence or presence of 5% H2O, Fourier transform infrared (FTIR) spectroscopy, as well as activity tests towards NO reduction by propene under the conditions of 3000 ppm NO, 3000 ppm C3H6, 1% O2, 0 or 10% H2O, and 50,000 h−1 space velocity. The objective was to investigate the influence of H2O addition on catalytic behavior. A good performance (100% NO conversion, 77% N2 yield, and 90% C3H6 conversion) was achieved at 600 °C over LaFe0.8Cu0.2O3 under a dry feed stream. With the exposure of LaFe0.8Cu0.2O3 to a humid atmosphere containing 10% water vapor, the catalytic activity was slightly decreased yielding 91% NO conversion, 51% N2 yield, and 86% C3H6 conversion. A competitive adsorption between H2O vapor with O2 and NO molecules at anion vacancies over LaFe0.8Cu0.2O3 was found by means of TPD studies here. A deactivation mechanism was therefore proposed involving the occupation of available active sites by water vapor, resulting in an inhibition of catalytic activity in C3H6 + NO + O2 reaction. This H2O deactivation was also verified to be strictly reversible by removing steam from the feed.  相似文献   

8.
Several hexaaluminate-related materials were prepared via hydrolysis of alkoxide and powder mixing method for high temperature combustion of CH4 and C3H8, in order to investigate the effect of the concentration of the fuels, O2 and H2O on NOx emission and combustion characteristics. Among the hexaaluminate catalysts, Sr0.8La0.2MnAl11O19− prepared by the alkoxide method exhibited the highest activity for methane combustion and low NOx emission capability. NOx emission at 1500 °C was increased linearly with O2 concentration, whereas water vapor addition decreased NOx emission in CH4 combustion over the Sr0.8La0.2MnAl11O19− catalyst. In the catalytic combustion of C3H8 over the Sr0.8La0.2MnAl11O19− catalyst, the amount of NOx emitted was raised in the temperature range between 1000 and 1500 °C when the C3H8 concentration increased from 1 to 2 vol.%. It was found that NOx emission in this temperature range was reduced effectively by adding water vapor.  相似文献   

9.
The catalytic activities of ceria-zirconia mixed oxides CexZr1−xO2 (x = 0.17, 0.42, 0.62 and 0.8) are determined by isothermal steady-state experiments using a representative mixture of exhaust gases of coal combustion. Results show that all supports are active in deNOx reaction in the presence of the previous hydrocarbons. However, their catalytic activity varies with the content of cerium and goes through a maximum for x = 0.62, leading to 27% NOx consumption. This activity was correlated with physicochemical properties determined by a linear solvation energy relationship (LSER) approach. Moreover, a mechanism of HC assisted reduction of NO is proposed on ceria-zirconia supported catalysts. This mechanism is divided in three catalytic cycles involving: (i) the oxidation of NO into NO2, (ii) the reaction of NO2 and the hydrocarbons leading to RNOx species and CxHyOz, and finally (iii) the decomposition of NO assisted by these latter CxHyOz species.  相似文献   

10.
A series of CoOx/Al2O3 catalysts was prepared, characterized, and applied for the selective catalytic reduction (SCR) of NO by C3H8. The results of XRD, UV–vis, IR, Far-IR and ESR characterizations of the catalysts suggest that the predominant oxidation state of cobalt species is +2 for the catalysts with low cobalt loading (≤2 mol%) and for the catalysts with 4 mol% cobalt loading prepared by sol–gel and co-precipitation. Co3O4 crystallites or agglomerates are the predominant species in the catalysts with high cobalt loading prepared by incipient wetness impregnation and solid dispersion. An optimized CoOx/Al2O3 catalyst shows high activity in SCR of NO by C3H8 (100% conversion of NO at 723 K, GHSV: 10,000 h−1). The activity of the selective catalytic reduction of NO by C3H8 increases with the increase of cobalt–alumina interactions in the catalysts. The influences of cobalt loading and catalyst preparation method on the catalytic performance suggest that tiny CoAl2O4 crystallites highly dispersed on alumina are responsible for the efficient catalytic reduction of NO, whereas Co3O4 crystallites catalyze the combustion of C3H8 only.  相似文献   

11.
Effect of substitution of CuO and WO3 on the microwave dielectric properties of BiNbO4 ceramics and the co-firing between ceramics and copper electrode were investigated. The (Bi1−xCux)(Nb1−xWx)O4 (x = 0.005, 0.01, 0.015, 0.02) composition can be densified between 900 and 990 °C. The microwave dielectric constants lie between 36 and 45 and the pores in ceramics were found to be the main influence. The Q values changes between 1400 and 2900 with different x values and sintering temperatures while Qf values lie between 6000 and 16,000 GHz. The microwave dielectric losses, mainly affected by the grain size, pores, and the secondary phase, are discussed. The (Bi1−xCux)(Nb1−xWx)O4 ceramics and copper electrode was co-fired under N2 atmosphere at 850 °C and the EDS analysis showed no reaction between the dielectrics and copper electrodes. This result presented the (Bi1−xCux)(Nb1−xWx)O4 dielectric materials to be good candidates for LTCC applications with copper electrode.  相似文献   

12.
The effect of the Pd addition method into the fresh Pd/(OSC + Al2O3) and (Pd + OSC)/Al2O3 catalysts (OSC material = CexZr1−xO2 mixed oxides) was investigated in this study. The CO + NO and CO + NO + O2 model reactions were studied over fresh and aged catalysts. The differences in the fresh catalysts were insignificant compared to the aged catalysts. During the CO + NO reaction, only small differences were observed in the behaviour of the fresh catalysts. The light-off temperature of CO was about 20 °C lower for the fresh Pd/(OSC + Al2O3) catalyst than for the fresh (Pd + OSC)/Al2O3 catalyst during the CO + NO + O2 reaction. For the aged catalysts lower NO reduction and CO oxidation activities were observed, as expected. Pd on OSC-containing alumina was more active than Pd on OSC material after the agings. The activity decline is due to a decrease in the number of active sites on the surface, which was observed as a larger Pd particle size for aged catalysts than for fresh catalysts. In addition, the oxygen storage capacity of the aged Pd/(OSC + Al2O3) catalyst was higher than that of the (Pd + OSC)/Al2O3 catalyst.  相似文献   

13.
The current work is devoted to study of CO interaction with PdO/Al2O3–(Cex–Zr1−x)O2 catalysts. Ceria–zirconia–alumina supports with different Ce/Zr ratio were prepared by sol–gel technique. The FT-IR characterization of CO adsorbed at −120 and 25 °C on oxidized and reduced samples revealed that Ce/Zr ratio modifies the surface properties of support and oxidation state of palladium. The catalyst with Ce/Zr molar ratio 0.5/0.5 was characterized with the highest ability to stabilize palladium in oxide state and the highest activity to oxidize CO. Redox treatment of catalysts improves their catalytic activity.  相似文献   

14.
The structural and electronic properties of selected compositions of SnxTi1−xO2 solid solutions (x=0, 1/24, 1/16, 1/12, 1/8, 1/6, 1/4, 1/2, 3/4, 5/6, 7/8, 11/12, 15/16, 23/24 and 1) were investigated by means of periodic density functional theory (DFT) calculations at B3LYP level. The calculations show that the corresponding lattice parameters vary non-linearly with composition, supporting positive deviations from Vegard’s law in the SnxTi1−xO2 system. Our results also account for the fact that chemical decomposition in SnxTi1−xO2 system is dominated by composition fluctuations along [0 0 1] direction. A nearly continuous evolution of the direct band gap and the Fermi level with the growing value of x is predicted. Ti 3d states dominate the lower portion of the conduction band of SnxTi1−xO2 solid solutions. Sn substitution for Ti in TiO2 increases the oxidation–reduction potential of the oxide as well as it renders the lowest energy transition to be indirect. These two effects can be the key factors controlling the rate for the photogenerated electron–hole recombination. These theoretical results are capable to explain the enhancement of photoactivity in SnxTi1−xO2 solid solutions.  相似文献   

15.
Supported LaCoO3 perovskites with 10 and 20 wt.% loading were obtained by wet impregnation of different Ce1−xZrxO2 (x = 0–0.3) supports with a solution prepared from La and Co nitrates, and citric acid. Supports were also prepared using the “citrate method”. All materials were calcined at 700 °C for 6 h and investigated by N2 adsorption at −196 °C, XRD and XPS. XRD patterns and XPS measurements evidenced the formation of a pure perovskite phase, preferentially accumulated at the outer surface. These materials were comparatively tested in benzene and toluene total oxidation in the temperature range 100–500 °C. All catalysts showed a lower T50 than the corresponding Ce1−xZrxO2 supports. Twenty weight percent LaCoO3 catalysts presented lower T50 than bulk LaCoO3. In terms of reaction rates per mass unit of perovskite calculated at 300 °C, two facts should be noted (i) the activity order is more than 10 times higher for toluene and (ii) the reverse variation with the loading as a function of the reactant, a better activity being observed for low loadings in the case of benzene. For the same loading, the support composition influences drastically the oxidative abilities of LaCoO3 by the surface area and the oxygen mobility.  相似文献   

16.
The CexZr1−xO2 solid solution was used as a support of a palladium catalyst for methanol decomposition to synthesis gas at low temperature. All Pd-containing catalysts tested in this study showed high selectivity to synthesis gas (over 96%). The Pd supported on the composite oxide with a Ce/Zr molar ratio of 4/1 exhibited the highest activity. Pd/Ce0.8Zr0.2O2 (17 wt.%) (cop) (prepared by coprecipitation method) showed a conversion of 51.2% for the methanol decomposition at 473 K, which was higher than those over 17 wt.% Pd/CeO2 (cop) (40.7%) and 17 wt.% Pd/ZrO2 (cop) (24.3%) at 473 K. The 17 wt.% Pd/Ce0.8Zr0.2O2 (cop) catalyst showed a higher BET surface area and smaller Pd particles than those of 17 wt.% Pd/CeO2 (cop). Moreover, a more active Pdσ+ state could be maintained by Zr4+ ion modification due to promotion of the oxygen mobility and enhancement of the reductibility and increase in the acid sites of the CeO2 support. The 17 wt.% Pd/Ce0.8Zr0.2O2 (cop) catalyst showed a much higher conversion (51.2%) than that over 17 wt.% Pd/Ce0.8Zr0.2O2 (imp) (prepared by impregnation method) (17.2%) at 473 K. This is due to the 17 wt.% Pd/Ce0.8Zr0.2O2 (cop) possessing many small Pd particles. The 17 wt.% Pd/Ce0.8Zr0.2O2 (cop) catalyst showed an initial conversion of 51.2% at 473 K but the conversion decreased to 43.1% after 24 h on stream. This deactivation was attributed to carbonaceous deposit on the catalyst surface. The amounts of coke on the 17 wt.% Pd/Ce0.8Zr0.2O2 (cop) catalyst were 0.9 wt.% after 24 h on stream at 473 K and 2.1 wt.% after 1 h on stream at 523 K.  相似文献   

17.
The aim of the present work is to obtain ceramic materials with a hexagonal structure and high density, hardness and mechanical strength at lower synthesis temperature. Ceramic samples with nominal composition La1−xCaxAl11−yzMgyTizO18 (x=0–1; y=0–3; z=0–3,5) are prepared. The samples are sintered at temperature 1500 °C by one-stage and two-stage ceramic technology. By X-ray diffraction and scanning electron microscopy, predominant phase LaAl11O18 and second phases LaAlO3 and -Al2O3 are identified. Ceramic materials are characterized with high physico-mechanical properties and may be find application for production of mill bodies and materials for immobilization of nuclear waste.  相似文献   

18.
CexTi1−xO2 oxides have been synthesised by sol–gel method with x varying from 0 to 0.3 and characterised by XRD and TPR. The structure of oxides changes with the Ce/Ti molar ratio. The presence of ceria in Ce-Ti oxides inhibits the phase transition from anatase to rutile. When x = 0.3 (Ce0.3Ti0.7O2 sample), the solid presents an amorphous state. The TPR results indicate that the presence of Ti enhances the reducibility of cerium oxide species. Catalytic oxidation of propene is investigated on Ce-Ti oxides and the better conversion is obtained with Ce0.3Ti0.7O2 but the CO2 selectivity reaches 63% at 400 °C. Gold is then deposited on theses oxides to improve the catalytic activity. On the basis of characterisation data (H2 TPR), it has been suggested that gold influences the reduction of the Ce-Ti oxide support and the catalytic activity to the propene oxidation. Thus, Au/Ce-Ti-O system catalysts are promising catalysts for propene oxidation.  相似文献   

19.
Catalytic methane combustion and CO oxidation were investigated over AFeO3 (A=La, Nd, Sm) and LaFe1−xMgxO3 (x=0.1, 0.2, 0.3, 0.4, 0.5) perovskites prepared by citrate method and calcined at 1073 K. The catalysts were characterized by X-ray diffraction (XRD). Redox properties and the content of Fe4+ were derived from temperature programmed reduction (TPR). Specific surface areas (SA) of perovskites were in 2.3–9.7 m2 g−1 range. XRD analysis showed that LaFeO3, NdFeO3, SmFeO3 and LaFe1−xMgxO3 (x·0.3) are single phase perovskite-type oxides. Traces of La2O3, in addition to the perovskite phase, were detected in the LaFe1−xMgxO3 catalysts with x=0.4 and 0.5. TPR gave evidence of the presence in AFeO3 of a very small fraction of Fe4+ which reduces to Fe3+. The fraction of Fe4+ in the LaFe1−xMgxO3 samples increased with increasing magnesium content up to x=0.2, then it remained nearly constant. Catalytic activity tests showed that all samples gave methane and CO complete conversion with 100% selectivity to CO2 below 973 and 773 K, respectively. For the AFeO3 materials the order of activity towards methane combustion is La>Nd>Sm, whereas the activity, per unit SA, of the LaFe1−xMgxO3 catalysts decreases with the amount of Mg at least for the catalysts showing a single perovskite phase (x=0.3). Concerning the CO oxidation, the order of activity for the AFeO3 materials is Nd>La>Sm, while the activity (per unit SA) of the LaFe1−xMgxO3 catalysts decreases at high magnesium content.  相似文献   

20.
Nanometer perovskite-type oxides La1−xSrxMO3−δ (M = Co, Mn; x = 0, 0.4) have been prepared using the citric acid complexing-hydrothermal-coupled method and characterized by means of techniques, such as X-ray diffraction (XRD), BET, high-resolution scanning electron microscopy (HRSEM), X-ray photoelectron spectroscopy (XPS), temperature-programmed desorption (TPD), and temperature-programmed reduction (TPR). The catalytic performance of these nanoperovskites in the combustion of ethylacetate (EA) has also been evaluated. The XRD results indicate that all the samples possessed single-phase rhombohedral crystal structures. The surface areas of these nanomaterials ranged from 20 to 33 m2 g−1, the achievement of such high surface areas are due to the uniform morphology with the typical particle size of 40–80 nm (as can be clearly seen in their HRSEM images) that were derived with the citric acid complexing-hydrothermally coupled strategy. The XPS results demonstrate the presence of Mn4+ and Mn3+ in La1−xSrxMnO3−δ and Co3+ and Co2+ in La1−xSrxCoO3−δ, Sr substitution induced the rises in Mn4+ and Co3+ concentrations; adsorbed oxygen species (O, O2, or O22−) were detected on the catalyst surfaces. The O2-TPD profiles indicate that Sr doping increased desorption of the adsorbed oxygen and lattice oxygen species at low temperatures. The H2-TPR results reveal that the nanoperovskite catalysts could be reduced at much lower temperatures (<240 °C) after Sr doping. It is observed that under the conditions of EA concentration = 1000 ppm, EA/oxygen molar ratio = 1/400, and space velocity = 20,000 h−1, the catalytic activity (as reflected by the temperature (T100%) for EA complete conversion) increased in the order of LaCoO2.91 (T100% = 230 °C) ≈ LaMnO3.12 (T100% = 235 °C) < La0.6Sr0.4MnO3.02 (T100% = 190 °C) < La0.6Sr0.4CoO2.78 (T100% = 175 °C); furthermore, there were no formation of partially oxidized by-products over these catalysts. Based on the above results, we conclude that the excellent catalytic performance is associated with the high surface areas, good redox properties (derived from higher Mn4+/Mn3+ and Co3+/Co2+ ratios), and rich lattice defects of the nanostructured La1−xSrxMO3−δ materials.  相似文献   

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