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1.
MnOx–CeO2 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 MnOx–CeO2 with Mn/(Mn + Ce) molar ratio of 0.5 exhibited the highest catalytic activity among the MnOx–CeO2 mixed oxides. Structure analysis by X-ray powder diffraction and temperature-programmed reduction of hydrogen revealed that the formation of MnOx–CeO2 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 MnOx–CeO2 mixed oxide indicated that both the Pt precursors and the reduction temperature greatly affected the catalytic performance. Pt/MnOx–CeO2 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 MnOx–CeO2 support.  相似文献   

2.
The reaction between hydrogen and NO was studied over 1 wt.% Pd supported on NOx-sorbing material, MnOx–CeO2, at low temperatures. The result of pulse mode reactions suggest that NOx adsorbed as nitrate and/or nitrite on MnOx–CeO2 was reduced by hydrogen, which was spilt-over from Pd catalyst. The NOx storage and reduction (NSR) cycles were carried out over Pd/MnOx–CeO2 in a conventional flow reactor at 150 °C. In a storage step, NO was removed by the oxidative adsorption from a stream of 0.04–0.08% NO, 5–10% O2, and He balance. This was followed by a reducing step, where a stream of 1% H2/He was supplied to ensure the conversion of nitrate/nitrite to N2 and thus restore the adsorbability. It was revealed that the NSR cycle is much more suitable for the H2–deNOx process in excess O2, compared to a conventional steady state reaction mode.  相似文献   

3.
Kinetic study of CO oxidation in combination with experiments of temperature-programmed oxidation (TPO) and reduction (TPR) have been performed on various unsupported crystalline manganese oxides (MnOx); while the reactivity shows an order of MnO ≤ MnO2 < Mn2O3 in a mixture of unit ratio of O2/CO at/below 523 K. We propose that under the current conditions the interaction of adsorbed CO and O is mainly responsible for CO2 formation on Mn2O3 and MnO2 catalysts, following either the Langmuir–Hinshelwood mechanism or Eley–Rideal mechanism. Meanwhile, direct evidence from transient CO oxidation suggests that the Mars-van-Krevelen mechanism may occur for all catalysts simultaneously, especially, it is predominant for the MnO catalyst. The evidence of structural modifications during reaction was confirmed by Raman spectra obtained from used MnO.  相似文献   

4.
Jun Fan  Xiaodong Wu  Lei Yang  Duan Weng   《Catalysis Today》2007,126(3-4):303-312
CeO2–ZrO2–La2O3 (CZL) mixed oxides were prepared by citric acid sol–gel method. The as-received gel was calcined at 500, 700, 900 and 1050 °C to obtain the so-called C5, C7, C9 and CK, respectively. The C5, C7 and C9 powders were impregnated with H2PtCl6 and then calcined at 500 °C to prepare P5C5, P5C7 and P5C9, respectively. The impregnated CK powders were calcined at 500, 700 and 900 °C to prepare P5CK, P7CK and P9CK, respectively. The XRD and XPS analyses show that the surface distribution of Pt is evidently influenced by the structural and textural properties of the support. The CO adsorption followed by FTIR reveals that the dispersion and the chemisorption sites of Pt are reduced as the calcination temperature of CZL support increases. The chemisorption ability of the CK samples is even completely deactivated. The encapsulation mechanism, which has been applied to explain the so-called strong metal–support interaction (SMSI) after reductive treatment, is introduced here to demonstrate the abnormal observations though the samples were prepared in oxidative atmosphere. The HRTEM results also confirm this explanation. The effects of oxygen vacancies, the chemisorption sites on the Pt surface and Pt/Ce interfacial sites on the three-way catalytic activities are discussed.  相似文献   

5.
Performances of BaTi1 − xNixO3 perovskites, prepared using sol–gel method, as catalysts for partial oxidation of methane to syngas have been studied. The catalysts were characterized by XRD, BET and TEM. The experimental studies showed the calcination temperature and Ni content exhibited a significant influence on catalytic activity. Among catalysts tested, the catalyst BaTi0.8Ni0.2O3 exhibited the best activity and excellent stability.  相似文献   

6.
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, Co3O4/CeO2 and Co3O4/CeO2–ZrO2 containing 30 wt.% of Co3O4. 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   


7.
The direct decomposition of nitric oxide (NO) over barium catalysts supported on various metal oxides was examined in the absence and presence of O2. Among the Ba catalysts supported on single-component metal oxides, Ba/Co3O4 and Ba/CeO2 showed high NO decomposition activities, while Ba/Al2O3, Ba/SiO2, and Ba/TiO2 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 CeO2–MnOx solid solutions with the cubic fluorite structure. O2-TPD of the CeO2–MnOx solid solutions showed a large desorption peak in a range of relatively low temperature. The BET surface areas of the CeO2–MnOx solid solutions were larger than those of pure CeO2 and Mn2O3. 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   

8.
Mesostructured MnOx–Cs2O–Al2O3 nanocomposites have been synthesized by reverse microemulsion method combined with hydrothermal treatment and then applied to the catalytic combustion of methane. Compared to impregnation-derived conventional MnOx/Cs2O/Com-Al2O3 catalyst, the microemulsion-derived catalyst showed higher activity and stability for methane combustion. The T10% of the fresh and of the 72 h aged MnxO–Cs2O–Al2O3 were 475 and 490 °C, respectively, recommending it as a potential candidate catalyst for application in hybrid gas turbines. The homogeneous composition of the microemulsion-derived nanocomposite catalyst can hinder the loss of Cs+ and accelerate the formation of Cs–β-alumina phase, ensuring thus higher activity and stability for methane combustion.  相似文献   

9.
The catalytic activity of a series of CeO2–ZrO2 mixed oxides in the total oxidation of methane and light hydrocarbons has been investigated. The influence of dopants like Mn and Cu has also been studied. It is shown that both MnOx and CuO at low loading dissolve within the ceria–zirconia lattice. This strongly influences the redox behaviour of the catalysts by promoting low-temperature reduction of Ce4+. In addition, the ternary oxides show better stability to repeated redox cycles, which is attributed to the presence of ZrO2. The catalytic activity of pure CeO2 is also enhanced in the presence of ZrO2, reaching a maximum with Ce0.92Zr0.08O2; a further promotion of activity is observed with the introduction of MnOx and CuO dissolved into CeO2–ZrO2 lattice.  相似文献   

10.
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   

11.
Co3O4/CeO2 composite oxides with different cobalt loading (5, 15, 30, 50, 70 wt.% as Co3O4) were prepared by co-precipitation method and investigated for the oxidation of methane under stoichiometric conditions. Pure oxides, Co3O4 and CeO2 were used as reference. Characterization studies by X-ray diffraction (XRD), BET, temperature programmed reduction/oxidation (TPR/TPO) and X-ray photoelectron spectroscopy (XPS) were carried out.

An improvement of the catalytic activity and thermal stability of the composite oxides was observed with respect to pure Co3O4 in correspondence of Co3O4–CeO2 containing 30% by weight of Co3O4. The combined effect of cobalt oxide and ceria, at this composition, strongly influences the morphological and redox properties of the composite oxides, by dispersing the Co3O4 phase and promoting the efficiency of the Co3+–Co2+ redox couple. The presence in the sample Co3O4(30 wt.%)–CeO2 of a high relative amount of Ce3+/(Ce4+ + Ce3+) as detected by XPS confirms the enhanced oxygen mobility.

The catalysts stability under reaction conditions was investigated by XRD and XPS analysis of the used samples, paying particular attention to the Co3O4 phase decomposition. Methane oxidation tests were performed over fresh (as prepared) and thermal aged samples (after ageing at 750 °C for 7 h, in furnace). The resistance to water vapour poisoning was evaluated for pure Co3O4 and Co3O4(30 wt.%)–CeO2, performing the tests in the presence of 5 vol.% H2O. A methane oxidation test upon hydrothermal ageing (flowing at 600 °C for 16 h a mixture 5 vol.% H2O + 5 vol.%O2 in He) of the Co3O4(30 wt.%)–CeO2 sample was also performed. All the results confirm the superiority of this composite oxide.  相似文献   


12.
CeO2 and CeReOx_y catalysts are prepared by the calcination at different temperatures (y = 500–1000 °C) and having a different composition (Re = La3+ or Pr3+/4+, 0–90 wt.%). The catalysts are characterised by XRD, H2-TPR, Raman, and BET surface area. The soot oxidation is studied with O2 and NO + O2 in the tight and loose contact conditions, respectively. CeO2 sinters between 800–900 °C due to a grain growth, leading to an increased crystallite size and a decreased BET surface area. La3+ or Pr3+/4+ hinders the grain growth of CeO2 and, thereby, improving the surface catalytic properties. Using O2 as an oxidant, an improved soot oxidation is observed over CeLaOx_y and CePrOx_y in the whole dopant weight loading and calcination temperature range studied, compared with CeO2. Using NO + O2, the soot conversion decreased over CeLaOx_y catalysts calcined below 800 °C compared with the soot oxidation over CeO2_y. CePrOx_y, on the other hand, showed a superior soot oxidation activity in the whole composition and calcination temperature range using NO + O2. The improvement in the soot oxidation activity over the various catalysts with O2 can be explained based on an improvement in the external surface area. The superior soot oxidation activity of CePrOx_y with NO + O2 is explained by the changes in the redox properties of the catalyst as well as surface area. CePrOx_y, having 50 wt.% of dopant, is found to be the best catalyst due to synergism between cerium and praseodymium compared to pure components. NO into NO2 oxidation activity, that determines soot oxidation activity, is improved over all CePrOx catalysts.  相似文献   

13.
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   

14.
The catalytic activity of Pt on alumina catalysts, with and without MnOx incorporated to the catalyst formulation, for CO oxidation in H2-free as well as in H2-rich stream (PROX) has been studied in the temperature range of 25–250 °C. The effect of catalyst preparation (by successive impregnation or by co-impregnation of Mn and Pt) and Mn content in the catalyst performance has been studied. A low Mn content (2 wt.%) has been found not to improve the catalyst activity compared to the base catalyst. However, catalysts prepared by successive impregnation with 8 and 15 wt.% Mn have shown a lower operation temperature for maximum CO conversion than the base catalyst with an enhanced catalyst activity at low temperatures with respect to Pt/Al2O3. A maximum CO conversion of 89.8%, with selectivity of 44.9% and CO yield of 40.3% could be reached over a catalyst with 15 wt.% Mn operating at 139 °C and λ = 2. The effect of the presence of 5 vol.% CO2 and 5 vol.% H2O in the feedstream on catalysts performance has also been studied and discussed. The presence of CO2 in the feedstream enhances the catalytic performance of all the studied catalysts at high temperature, whereas the presence of steam inhibits catalysts with higher MnOx content.  相似文献   

15.
The NiSO4 supported on Fe2O3-promoted ZrO2 catalysts were prepared by the impregnation method. Fe2O3-promoted ZrO2 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 Fe2O3–ZrO2. The addition of nickel sulfate (or Fe2O3) to ZrO2 shifted the phase transition of ZrO2 (from amorphous to tetragonal) to higher temperatures because of the interaction between nickel sulfate (or Fe2O3) and ZrO2. 15-NiSO4/5-Fe2O3–ZrO2 containing 15 wt.% NiSO4 and 5 mol% Fe2O3, and calcined at 500 °C exhibited a maximum catalytic activity for ethylene dimerization. NiSO4/Fe2O3–ZrO2 catalysts was very effective for ethylene dimerization even at room temperature, but Fe2O3–ZrO2 without NiSO4 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 Fe2O3 up to 5 mol% enhanced the acidity, surface area, thermal property, and catalytic activities of catalysts gradually, due to the interaction between Fe2O3 and ZrO2 and due to consequent formation of Fe–O–Zr bond.  相似文献   

16.
The catalytic performance of mono- and bimetallic Pd (0.6, 1.0 wt.%)–Pt (0.3 wt.%) catalysts supported on ZrO2 (70, 85 wt.%)–Al2O3 (15, 0 wt.%)–WOx (15 wt.%) prepared by sol–gel was studied in the hydroisomerization of n-hexane. The catalysts were characterized by N2 physisorption, XRD, TPR, XPS, Raman, NMR, and FT-IR of adsorbed pyridine. The preparation of ZrW and ZrAlW mixed oxides by sol–gel favored the high dispersion of WOx and the stabilization of zirconia in the tetragonal phase. The Al incorporation avoided the formation of monoclinic-WO3 bulk phase. The catalysts increased their SBET for about 15% promoted by Al2O3 addition. Various oxidation states of WOx species coexist on the surface of the catalysts after calcination. The structure of the highly dispersed surface WOx species is constituted mainly of isolated monotungstate and two-dimensional mono-oxotungstate species in tetrahedral coordination. The activity of Pd/ZrW catalysts in the hydroisomerization of n-hexane is promoted both with the addition of Al to the ZrW mixed oxide and the addition of Pt to Pd/ZrAlW catalysts. The improvement in the activity of Pd/ZrAlW catalysts is ascribed to a moderated acid strength and acidity, which can be correlated to the coexistence of W6+ and reduced-state WOx species (either W4+ or W0). The addition of Pt to the Pd/ZrAlW catalyst does not modify significantly its acidic character. Selectivity results showed that the catalyst produced 2MP, 3MP and the high octane 2,3-dimethylbutane (2,3-DMB) and 2,2-dimethylbutane (2,2-DMB) isomers.  相似文献   

17.
Ceria (CeO2) and rare-earth modified ceria (CeReOx with Re = La, Pr, Sm, Y) catalysts are prepared by nitrate precursor calcination and are characterised by BET surface area, XRD, H2-TPR, and Raman spectroscopy. Potential of the catalysts in the soot oxidation is evaluated in TGA with a feed gas containing O2. Seven hundred degree Celsius calcination leads to a decrease in the surface area of the rare-earth modified CeO2 compared with CeO2. However, an increase in the meso/macro pore volume, an important parameter for the soot oxidation with O2, is observed. Rare-earth ion doping led to the stabilisation of the CeO2 surface area when calcined at 1000 °C. XRD, H2-TPR, and Raman characterisation show a solid solution formation in most of the mixed oxide catalysts. Surface segregation of dopant and even separate phases, in CeSmOx and CeYOx catalysts, are, however, observed. CePrOx and CeLaOx catalysts show superior soot oxidation activity (100% soot oxidation below 550 °C) compared with CeSmOx, CeYOx, and CeO2. The improved soot oxidation activity of rare-earth doped CeO2 catalysts with O2 can be correlated with the increased meso/micro pore volume and stabilisation of external surface area. The segregation of the phases and the enrichment of the catalyst surface with unreducible dopant decrease the intrinsic soot oxidation activity of the potential CeO2 catalytic sites. Doping CeO2 with a reducible ion such as Pr4+/3+ shows an increase in the soot oxidation. However, the ease of catalyst reduction and the bulk oxygen-storage capacity is not a critical parameter in the determination of the soot oxidation activity. During the soot oxidation with O2, the function of the catalyst is to increase the ‘active oxygen’ transfer to the soot surface, but it does not change the rate-determining step, as evident from the unchanged apparent activation energy (around 150 kJ mol−1), for the catalysed and un-catalysed soot oxidation. Spill over of oxygen on the soot surface and its subsequent adsorption at the active carbon sites is an important intermediate step in the soot oxidation mechanism.  相似文献   

18.
A novel CeO2–Y2O3 (CY) washcoat on cordierite honeycomb was prepared by an impregnation method, which was used as a support to prepare a Pd catalyst. A model reaction of the complete combustion of toluene was conducted to evaluate the performance of the developed Pd/CY catalyst. The CY washcoat support and the Pd/CY catalyst were characterized by XRD, Raman spectroscopy, H2-TPR and SEM techniques. The results show that compared with conventional washcoat the CY washcoat has better adhesion and higher vibration- and heat-resistance. The CY washcoat can anchor well Pd onto the cordierite honeycomb substrate. The formation of a CeO2–Y2O3 solid solution and the steady present of PdO occur at high calcination temperatures, resulting in a better thermal stability. On a Pd/CY catalyst calcined at 500 °C, a 99% of toluene conversion was obtained at 210 °C, and it was stable for reaction time up to 30 h.  相似文献   

19.
The effect of CeO2 loading (1–20 wt.%) on the properties and catalytic behaviors of CeO2–Al2O3-supported Pt catalysts on the partial oxidation of methane was studied. The catalysts were characterized by SBET, X-ray diffraction (XRD), temperature-programmed reduction (TPR) and oxygen storage capacity (OSC). XRD and TPR results showed that the pretreatment temperature of the support influences on the amount of CeO2 with fluorite structure. The pretreatment temperature of the support and CeO2 loading influenced the morphology of Pt. OSC analysis showed a significant increase in the oxygen storage capacity per weight of CeO2 for samples with high CeO2 loading (12 and 20 wt.%). TPR analyses showed that the addition of Pt promotes the reduction of CeO2. This effect was more significant for the catalysts with high CeO2 loading (≥12 wt.%). The dispersion of Pt, measured by the rate of cyclohexane dehydrogenation, increases with increasing of the pretreatment temperature of the support. It was shown that the kind of the support is very important for obtaining of catalysts resistant to carbon formation. The catalysts with high CeO2 loading (≥12 wt.%) showed the highest catalytic activity and stability in the reaction of partial oxidation of methane due to a higher Pt–CeO2 interface.  相似文献   

20.
The performance of unpromoted and MOx-(M: alkali (earth), transition metal and cerium) promoted Au/Al2O3 catalysts have been studied for combustion of the saturated hydrocarbons methane and propane. As expected, higher temperatures are required to oxidize CH4 (above 400 °C), compared with C3H8 (above 250 °C). The addition of various MOx to Au/Al2O3 improves the catalytic activity in both methane and propane oxidation. For methane oxidation, the most efficient promoters to enhance the catalytic performance of Au/Al2O3 are FeOx and MnOx. For C3H8 oxidation a direct relationship is found between the catalytic performance and the average size of the gold particles in the presence of alkali (earth) metal oxides. The effect of the gold particle size becomes less important for additives of the type of transition metal oxides and ceria. The results suggest that the role of the alkali (earth) metal oxides is related to the stabilization of the gold nanoparticles, whereas transition metal oxide and ceria additives may be involved in oxygen activation.  相似文献   

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