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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 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   

3.
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   

4.
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   

5.
NO conversion to N2 in the presence of methane and oxygen over 0.03 at.%Rh/Al2O3, 0.51 at.%Pt/Al2O3 and 0.34 at.%Pt–0.03 at.%Rh/Al2O3 catalysts was investigated.

δ-Alumina and precious metal–aluminum alloy phases were revealed by XRD and HRTEM in the catalysts.

The results of the catalytic activity investigations, with temperature-programmed as well as steady-state methods, showed that NO decomposition occurs at a reasonable rate on the alloy surfaces at temperatures up to 623 K whereas some CH4 deNOx takes place on δ-alumina above this temperature. A mechanism for the NO decomposition is proposed herein. It is based on NO adsorption on the precious metal atoms followed by the transfer of electrons from alloy to antibonding π orbitals of NO(ads.) molecules. The CH4 deNOx was shown to occur according to an earlier proposed mechanism, via methane oxidation by NO2(ads.) to oxygenates and then NO reduction by oxygenates to N2.  相似文献   


6.
Pt–Ba–Al2O3 active and selective for NOx storage and selective reduction to N2 has been prepared and tested. Characterization of the parent Al2O3, Pt–Al2O3 and Ba–Al2O3 materials, as well as of Pt–Ba–Al2O3 catalyst in the oxidized, reduced and sulphated state has been performed by FT-IR spectroscopy of low-temperature adsorbed carbon monoxide and of adsorbed acetonitrile. XRD, TEM and XPS analyses have also been performed. Evidence for the predominance of Ba species, which are highly dispersed on the alumina support surface, and may be carbonated or sulphated, has been provided. Competitive interaction of Pt and Ba species with the surface sites of alumina has also been found.  相似文献   

7.
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   

8.
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   

9.
Catalytic performance of Sn/Al2O3 catalysts prepared by impregnation (IM) and sol–gel (SG) method for selective catalytic reduction of NOx by propene under lean burn condition were investigated. The physical properties of catalyst were characterized by BET, XRD, XPS and TPD. The results showed that NO2 had higher reactivity than NO to nitrogen, the maximum NO conversion was 82% on the 5% Sn/Al2O3 (SG) catalyst, and the maximum NO2 conversion reached nearly 100% around 425 °C. Such a temperature of maximum NO conversion was in accordance with those of NOx desorption accompanied with O2 around 450 °C. The activity of NO reduction was enhanced remarkably by the presence of H2O and SO2 at low temperature, and the temperature window was also broadened in the presence of H2O and SO2, however the NOx desorption and NO conversion decreased sharply on the 300 ppm SO2 treated catalyst, the catalytic activity was inhibited by the presence of SO2 due to formation of sulfate species (SO42−) on the catalysts. The presence of oxygen played an essential role in NO reduction, and the activity of the 5% Sn/Al2O3 (SG) was not decreased in the presence of large oxygen.  相似文献   

10.
A series of LaAl11O18- and Al2O3-supported LaCrO3 and Cr2O3 combustion catalysts was prepared. Different active phase–support combinations were prepared and applied to cordierite monoliths. The washcoat materials were aged in flowing humid air at temperatures between 1100°C and 1400°C, after which they were characterized by BET, XRD, TPR, and EDS. The monolith catalysts were evaluated in methane combustion. The presence of an active phase retarded sintering of the Al2O3 support, whereas the active phase slightly decreased the thermal stability of LaAl11O18. X-ray measurements revealed extensive interaction between support and active phase in the washcoat materials. A substituted perovskite, LaCr1−xAlxO3, is proposed to be formed in nearly all samples containing both lanthanum and chromium. The accessibility of chromium decreased rapidly after aging. The activities of the Al2O3-supported catalysts were higher than of those supported on LaAl11O18, which was related to the higher surface area of the former.  相似文献   

11.
MnOx–CeO2 mixed oxides prepared by sol–gel method, coprecipitation method and modified coprecipitation method were investigated for the complete oxidation of formaldehyde. Structure analysis by H2-TPR and XPS revealed that there were more Mn4+ 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 MnOx–CeO2 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 MnOx–CeO2 solid solution. While the diffraction peaks corresponding to MnO2 phase in the samples calcined above 773 K were clearly observed, indicating the occurrence of phase segregation between MnO2 and CeO2. Accordingly, it was supposed that the strong interaction between MnOx and CeO2, 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   

12.
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   

13.
The effect of Al2O3 levels on the properties of NiO in coprecipitated NiO–Al2O3 samples were investigated, using samples with up to 60.7 wt.% Al2O3 that had been calcined in the range 300–700°C. Characterization techniques included BET surface area of fresh and reduced catalysts, X-ray diffraction analysis of structure and crystallite size, magnetic susceptibility measurements, oxidizing power, and reducibility in H2. Only NiO was detected in samples with up to 4.1 wt.% Al2O3 for all sample calcination temperatures. Surface areas were similar for all fresh samples but decreased rapidly after calcination at high temperatures. The surface area loss was less for the higher Al2O3-containing samples. Nickel oxide crystallite sizes increased at higher calcination temperatures, but remained approximately the same for each Al2O3 level.

The NiO was nonstoichiometric (NiO1+x), with x decreasing at higher calcination temperatures and increasing with small amounts of added Al2O3 through a maximum at about 3 wt.% Al2O3. However, this did not correlate well with microstrain in the NiO crystallites nor with reducibility, which decreased with Al2O3 addition. At higher levels of Al2O3 (13.6 wt.% and above), surface areas increased with higher Al2O3 loadings, but NiO crystallite sizes remained approximately the same, independent of both Al2O3 content and calcination temperature. X-ray diffraction patterns were very diffuse, and it was not possible to rule out the presence of pseudo-spinel combinations of NiO and Al2O3. Reducibility was more difficult than with low Al2O3 levels, and nonstoichiometry was low and independent of Al2O3 content.

Reducibilities of all samples calcined at 300°C correlated well with the final BET surface area of the reduced samples, indicating that more dispersed NiO crystallites are more difficult to reduce, a conclusion that supports a model for reduction proposed previously.  相似文献   


14.
Water–gas shift reaction was studied over two nanostructured CuxCe1−xO2−y catalysts: a Cu0.1Ce0.9O2−y catalyst prepared by a sol–gel method and a Cu0.2Ce0.8O2−y catalyst prepared by co-precipitation method. A commercial low temperature water–gas shift CuO–ZnO–Al2O3 catalyst was used as reference. The kinetics was studied in a plug flow micro reactor at an atmospheric pressure in the temperature interval between 298 and 673 K at two different space velocities: 5.000 and 30.000 h−1, respectively. Experimentally estimated activation energy, Eaf, of the forward water–gas shift reaction at CO/H2O = 1/3 was 51 kJ/mol over the Cu0.1Ce0.9O2−y, 34 kJ/mol over the Cu0.2Ce0.8O2−y and 47 kJ/mol over the CuO–ZnO–Al2O3 catalyst. A simple rate expression approximating the water–gas shift process as a single reversible surface reaction was used to fit the experimental data in order to evaluate the rate constants of the forward and backward reactions and of the activation energy for the backward reaction.  相似文献   

15.
Zirconia supported on alumina was prepared and characterized by BET surface area, X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), temperature programmed desorption (TPD), and pulse reaction. 0.2% Pd/ZrO2/Al2O3 catalyst were prepared by incipient wetness impregnation of supports with aqueous solution of Pd(NO3)2. The effects of support properties on catalytic activity for methane combustion and CO oxidation were investigated. The results show that ZrO2 is highly dispersed on the surface of Al2O3 up to 10 wt.% ZrO2, beyond this value tetragonal ZrO2 is formed. The presence of a small amount of ZrO2 can increase the surface area, pore volume and acidity of support. CO–TPD results show that the increase of CO adsorption capacity and the activation of CO bond after the presence of ZrO2 lead to the increase of catalytic activity of Pd catalyst for CO oxidation. CO pulse reaction results indicate that the lattice oxygen of support can be activated at lower temperature following the presence of ZrO2, but it does not accelerate the activity of 0.2% Pd/ZrO2/Al2O3 for methane combustion. 0.2% Pd/ZrO2/Al2O3 dried at 120 °C shows highest activity for CH4 combustion, and the activity can be further enhanced following the repeat run. The increase of treatment temperature and pre-reduction can decrease the activity of catalyst for CH4 combustion.  相似文献   

16.
A multi-component NOx-trap catalyst consisting of Pt and K supported on γ-Al2O3 was studied at 250 °C to determine the roles of the individual catalyst components, to identify the adsorbing species during the lean capture cycle, and to assess the effects of H2O and CO2 on NOx storage. The Al2O3 support was shown to have NOx trapping capability with and without Pt present (at 250 °C Pt/Al2O3 adsorbs 2.3 μmols NOx/m2). NOx is primarily trapped on Al2O3 in the form of nitrates with monodentate, chelating and bridged forms apparent in Diffuse Reflectance mid-Infrared Fourier Transform Spectroscopy (DRIFTS) analysis. The addition of K to the catalyst increases the adsorption capacity to 6.2 μmols NOx/m2, and the primary storage form on K is a free nitrate ion. Quantitative DRIFTS analysis shows that 12% of the nitrates on a Pt/K/Al2O3 catalyst are coordinated on the Al2O3 support at saturation.

When 5% CO2 was included in a feed stream with 300 ppm NO and 12% O2, the amount of K-based nitrate storage decreased by 45% after 1 h on stream due to the competition of adsorbed free nitrates with carboxylates for adsorption sites. When 5% H2O was included in a feed stream with 300 ppm NO and 12% O2, the amount of K-based nitrate storage decreased by only 16% after 1 h, but the Al2O3-based nitrates decreased by 92%. Interestingly, with both 5% CO2 and 5% H2O in the feed, the total storage only decreased by 11%, as the hydroxyl groups generated on Al2O3 destabilized the K–CO2 bond; specifically, H2O mitigates the NOx storage capacity losses associated with carboxylate competition.  相似文献   


17.
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   

18.
Ni catalysts supported on γ-Al2O3, CeO2 and CeO2–Al2O3 systems were tested for catalytic CO2 reforming of methane into synthesis gas. Ni/CeO2–Al2O3 catalysts showed much better catalytic performance than either CeO2- or γ-Al2O3-supported Ni catalysts. CeO2 as a support for Ni catalysts produced a strong metal–support interaction (SMSI), which reduced the catalytic activity and carbon deposition. However, CeO2 had positive effect on catalytic activity, stability, and carbon suppression when used as a promoter in Ni/γ-Al2O3 catalysts for this reaction. A weight loading of 1–5 wt% CeO2 was found to be the optimum. Ni catalysts with CeO2 promoters reduced the chemical interaction between nickel and support, resulting in an increase in reducibility and stronger dispersion of nickel. The stability and less coking on CeO2-promoted catalysts are attributed to the oxidative properties of CeO2.  相似文献   

19.
The effectiveness of Ag/Al2O3 catalyst depends greatly on the alumina source used for preparation. A series of alumina-supported catalysts derived from AlOOH, Al2O3, and Al(OH)3 was studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet–visible (UV–vis) spectroscopy, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, O2, NO + O2-temperature programmed desorption (TPD), H2-temperature programmed reduction (TPR), thermal gravimetric analysis (TGA) and activity test, with a focus on the correlation between their redox properties and catalytic behavior towards C3H6-selective catalytic reduction (SCR) of NO reaction. The best SCR activity along with a moderated C3H6 conversion was achieved over Ag/Al2O3 (I) employing AlOOH source. The high density of Ag–O–Al species in Ag/Al2O3 (I) is deemed to be crucial for NO selective reduction into N2. By contrast, a high C3H6 conversion simultaneously with a moderate N2 yield was observed over Ag/Al2O3 (II) prepared from a γ-Al2O3 source. The larger particles of AgmO (m > 2) crystallites were believed to facilitate the propene oxidation therefore leading to a scarcity of reductant for SCR of NO. An amorphous Ag/Al2O3 (III) was obtained via employing a Al(OH)3 source and 500 °C calcination exhibiting a poor SCR performance similar to that for Ag-free Al2O3 (I). A subsequent calcination of Ag/Al2O3 (III) at 800 °C led to the generation of Ag/Al2O3 (IV) catalyst yielding a significant enhancement in both N2 yield and C3H6 conversion, which was attributed to the appearance of γ-phase structure and an increase in surface area. Further thermo treatment at 950 °C for the preparation of Ag/Al2O3 (V) accelerated the sintering of Ag clusters resulting in a severe unselective combustion, which competes with SCR of NO reaction. In view of the transient studies, the redox properties of the prepared catalysts were investigated showing an oxidation capability of Ag/Al2O3 (II and V) > Ag/Al2O3 (IV) > Ag/Al2O3 (I) > Ag/Al2O3 (III) and Al2O3 (I). The formation of nitrate species is an important step for the deNOx process, which can be promoted by increasing O2 feed concentration as evidenced by NO + O2-TPD study for Ag/Al2O3 (I), achieving a better catalytic performance.  相似文献   

20.
The behaviour of a Pt(1 wt.%) supported on CeO2–ZrO2(20 wt.%)/Al2O3(64 wt.%)–BaO(16 wt.%) as a novel NOx storage–reduction catalyst is studied by reactivity tests and DRIFT experiments and compared with that of Pt(1%)–BaO(15 wt.%) on alumina. The former catalyst, designed as a hydrothermally stable sample, is composed of an alumina modified with Ba ions and an overlayer of ceria-zirconia. The results pointed out that during the calcination barium ions migrates over the surface of the catalyst which thus show a good NOx storage–reduction behaviour comparable with that of Pt–BaO on alumina, although Ba ions result much better dispersed.  相似文献   

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