首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
MnO and CeO2 powders were mechanically mixed by a spatula and by milling to obtain loose-contact and tight-contact mixed oxides,respectively.The monoxides and their physical mixtures were characterized by X-ray diffraction(XRD),Brunauer-Emmett-Teller(BET),X-ray photoelectron spectroscopy(XPS),Raman,O2 temperature-programmed desorption(O2-TPD),H2 temperature-programmed reduction(H2-TPR) and NO temperature-programmed oxidation(NO-TPO).The MnOx-CeO2 solid solutions did not form without any calcination process.The oxidation state of manganese tended to increase while the ionic valence of cerium decreased in the mixed oxides,accompanied with the formation of oxygen vacancies.This long-ranged electronic interaction occured more significantly in the tight-contact mixture of MnO and CeO2.The formation of more Mn4+and oxygen vacancies promoted the catalytic oxidation of NO in an oxygen-rich atmosphere.  相似文献   

2.
A series of La1‒xSrxMnO3 samples were prepared by sol–gel method and used to degrade rhodamine B (RhB) in water. All samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 adsorption–desorption, temperature-programmed reduction of H2 (H2-TPR) and temperature-programmed desorption of O2 (O2-TPD). The results show that the degradation of RhB is highly dependent on the initial pH value of solution. Sr doping enhances the degradation ability of LaMnO3 for RhB in the time range of 0–40 min under a strong acidic environment, but all samples exhibit similar degradation rate from 40 to 60 min. In La0.7Sr0.3MnO3–RhB reaction system, there are two different degradation pathways, including N-de-ethylation, chromophore cleavage, ring-opening and mineralization. La1‒xSrxMnO3 (x ≤ 0.3) has the perovskite structure of La–Mn oxides, while La0.6Sr0.4MnO3 exhibits a Sr0.4MnLa0.6O2.98 perovskite phase. Sr doping leads to distortion of rhombohedral crystal structure and increases the relative content of Mn4+. The perovskite structure is stable in strong acidic environment during RhB degradation, but the relative content of Mn4+ and Mn3+ on the material surface changes. Sr doped LaMnO3 achieves specific surface area of 58.8 m2/g and total pore volume of 0.152 cm3/g. Furthermore, Sr2+ doping improves redox properties of La–Mn oxides, and the presence of defects makes oxygen diffusion easier compared with the undoped samples.  相似文献   

3.
The NO oxidation reaction was studied over MnOx-CeO2 catalysts prepared by co-precipitation, impregnation and mechanical mixing method, respectively. It was found that the co-precipitation was the most active and a 60% NO conversion was achieved at 250 °C. X-ray diffraction (XRD), Brumauer-Emmett (BET), H2-temperature programmed reduction (H2-TPR) and oxygen storage capacity (OSC) techniques were employed to characterize the physical and chemical properties of the catalysts. XRD results showed that amorphous MnOx or Mn-O-Ce solid solution existed in co-precipitation and impregnation prepared sample, while crystalline MnOx was found in mechanical mixing catalyst. A larger surface area was observed on co-precipitation prepared catalyst compared to those prepared by impregnation and mechanical mixing. The strong interaction between MnOx and CeO2 enhanced the reducibility of the oxides and increased the amount of Mn4+ and activated oxygen, which are favorable for NO oxidation to NO2.  相似文献   

4.
A series of La_(1-x)Ce_xMnO_(3+δ)(x=D,0.05,0.1,0.2,and 0.3) perovskites and Mn-Ce mixed oxides were prepared.Their physico-chemical properties were systematically characterized and the NO oxidation activities of the catalysts were investigated.The La_(0.9)Ce_(0.1)MnO_(3+δ) has the best activity among all of the catalysts,with a maximum NO conversion of 85% at 300℃.The characterization results indicate that the doping of Ce improves the properties of the perovsidtes in terms of the specific surface area,the average valence state of Mn ions,the number of reactive oxygen species and the NO_x desorption behaviors.The Mn-Ce mixed oxide calcined at 500℃ shows a similar NO oxidation activity with La_(0.9)Ce_(0.1)MnO_(3+δ).However,the activity of the mixed oxide obtained at 750℃ decreases a lot,which results from the loss of active sites and active oxygen species.  相似文献   

5.
The CuO/CeO2 catalysts were investigated by means of X-ray diffraction(XRD),laser Raman spectroscopy(LRS),X-ray photoelectronic spectroscopy(XPS),temperature-programmed reduction(TPR),in situ Fourier transform infrared spectroscopy(FTIR) and NO+CO reaction.The results revealed that the low temperature(150 °C) catalytic performances were enhanced for CO pretreated samples.During CO pretreatment,the surface Cu+/Cu0 and oxygen vacancies on ceria surface were present.The low valence copper species activated the adsorbed CO and surface oxygen vacancies facilitated the NO dissociation.These effects in turn led to higher activities of CuO/CeO2 for NO reduction.The current study provided helpful understandings of active sites and reaction mechanism in NO+CO reaction.  相似文献   

6.
In order to investigate the influence of MnO2 modification methods on the catalytic performance of CuO/CeO2 catalyst for NO reduction by CO,two series of catalysts(xCuyMn/Ce and xCu/yMn/Ce) were prepared by co-impregnation and stepwise-impregnation methods,and characterized by means of X-ray diffraction(XRD),Raman spectra,H2-temperature programmed reduction(H2-TPR),in situ diffuse reflectance infrared Fourier transform spectra(in situ DRIFTS) techniques.Furthermore,the catalytic performances of these catalysts were evaluated by NO+CO model reaction.The obtained results indicated that:(1) The catalysts acquired by co-impregnation method exhibited stronger interaction owing to the more sufficient contact among each component of the catalysts compared with the catalysts obtained by stepwise-impregnation method,which was beneficial to the improvement of the reduction behavior;(2) The excellent reduction behavior was conducive to the formation of low valence state copper species(Cu+/Cu0) and more oxygen vacancies(especially the surface synergetic oxygen vacancies(SSOV,Cu+-□-Mn(4–x)+)) during the reaction process,which were beneficial to the adsorption of CO species and the dissociation of NO species,respectively,and further promoted the enhancement of the catalytic performance.Finally,in order to further understand the difference between the catalytic performances of these catalysts prepared by co-impregnation and stepwise-impregnation methods,a possible reaction mechanism(schematic diagram) was tentatively proposed.  相似文献   

7.
Hierarchical ZSM-5(HZ) molecular sieves based on fly ash were synthesized using a method combining water heat treatment with step-by-step calcination.The coupling catalysts between La_(1-x)Ce_xMn_(0.8)-Ni_(0.2)O_3(x ≤ 0.5) perovskites and HZ were prepared through the impregnation method,which were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),high-resolution transmission electron microscopy(HRTEM),N_2 adsorption,X-ray photoelectron spectroscopy(XPS),NH_3-temperature programmed desoprtion(NH_3-TPD),H_2-temperature programmed reduction(H_2-TPR) and O_2-TPD techniques and investigated regarding pentanal oxidation at 120-390℃ to explore the effects of Ce doping on the catalytic activity and the active oxygen species of the coupling catalysts,meanwhile,the reaction mechanism and pathway of pentanal oxidation were also studied.The results reveal that Ce substitution at La sites can change the electronic interactions between all the elements and promote the electronic transfer among La,Ce,Ni,Mn and HZ,influencing directly the physicochemical characteristics of the catalysts.Moreover,the amount and transfer ability of surface adsorbed oxygen(O_2~-and O~-)regarded as the reactive oxygen species and the low temperature reducibility are the main influence factors in pentanal oxidation.Additionally,La_(0.8)Ce_(0.2)Mn_(0.8)Ni_(0.2)O_3/HZ exhibits the best catalytic activity and deep oxidation capacity as well as a better water resistance due to its larger amount of surface adsorbed oxygen species and higher low temperature reducibility.What's more,appropriate Ce substitution can significantly enhance the amount of O_2~-ions,which can distinctly enhance the catalytic activity of the catalyst,and moderate acid strength and appropriate acid amount can also facilitate the improvement of the pentanal oxidation activity.It is found that there is a synergic catalytic effect between surface acidity and redox ability of the catalyst.According to the in situ DRIFTS and GC/MS analyses,pentanal can be oxidized gradually to CO_2 and H_2 O by the surface oxygen species with the form of adsorption in air following the Langmuir-Hinshelwood(L-H) reaction mechanism.Two reaction pathways for the pentanal oxidation process are proposed,and the conversion of the formates to carbonates may be one of the main rate-determining steps.  相似文献   

8.
Herein,we report the high De-NO_x performance of the A-site defective perovskite-based Pd/La_(0.5)Sr_(0.3)MnO_3 catalyst.The formation of the defective perovskite structure can be proved by both the increased Mn~(4+)/Mn~(3+) ratio and serious lattice contraction due to cationic nonstoichiometry.It promotes the Sr doping into perovskite lattice and reduces the formation of the SrCO_3 phase.Our results demonstrate that below 300℃ the A-site defective perovskite can be more efficiently regenerated than the SrCO_3 phase as NO_x storage sites due to the latter's stronger basicity,and also exhibits the higher NO oxidation ability than the A-site stoichiometric and excessive catalysts.Both factors promote the lowtemperature De-NO_x activity of the Pd/La_(0.5)Sr_(0.3)MnO_3 catalyst through improving its NO_x trapping efficiency.Nevertheless,above 300℃,the NO_x reduction becomes the determinant of the De-NO_x activity of the perovskite-based catalysts.A-site defects can weaken the interactions between perovskite and Pd,inducing activation of Pd sites by in-situ transformation from PdO to metallic Pd in the alternative leanburn/fuel-rich atmospheric alternations,which boosts the De-NO_x activity of the Pd/La_(0.5)Sr_(0.3)MnO_3 catalyst.The Pd/L_(0.5)Sr_(0.3)MnO_3 catalyst exhibits the high sulfur tolerance as well.These findings provide insight into optimizing the structural properties and catalytic activities of the perovskite-based catalysts via tuning formulation,and have potential to be applied for various related catalyst systems.  相似文献   

9.
The disordered macroporous-mesoporous La_(1-x)Ce_xCoO_3 catalysts were prepared by complexcombustion method with ethylene glycol as complexing agent at relatively low calcination temperature.The samples were characterized by means of X-ray diffraction,N2 adsorption-ndash;desorption,Xray photoelectron spectroscopy,transmission electron microscopy,hydrogen temperature-programmed reduction and soot temperature-programmed reduction,and so on.The results show that the use of complexing agent and relatively low calcination temperature increase the specific surface area of the catalyst and have abundant pore structure.The Ce ions introduced into lattice of LaCoO_3 mainly exist in the form of tetravalent.At the same time,Ce ions enhance the redox performance of the catalyst and the mobility of active oxygen species,which enhances the catalytic activity of the catalyst for soot combustion.The results of activity test show that La_(0.9)Ce_(0.1)CoO_3 catalyst exhibits the highest activity in the absence of NO and NO_2,and its T_(10),T_(50) and T_(90) are 371,444,and 497℃,respectively.At the same time,a possible reaction mechanism is proposed in this study based on the turnover frequency(TOF) calculated by isothermal anaerobic titrations,XPS and XRD results.  相似文献   

10.
A series of three-dimensionally ordered macro-mesoporous(3DOMM) La_(1-x)Ca_xFeO_3(x=0-0.3)perovskite-type oxides were designed and successfully fabricated for the first time via a dual-template method.In which,PMMA and Brij-56 were employed as the hard template and soft template,respectively.It is found that 3 DOMM La_(1-x)Ca_xFeO_3 exhibits abundant wormlike mesoporous channels about 3 nm in diameter on macroporous skeleton walls.The excellent catalytic activity of soot combustion benefits from not only the well-designed hierarchical porous structure of catalyst,but also the redox electron pair of Fe~(3+)/Fe~(4+) induced by the doping of low-valent alkaline earth metal Ca to A-site of LaFeO_3.3DOMM La_(0.8)Ca_(0.2)FeO_3 exhibits superior catalytic performance for soot combustion,which shows T_(50) of396℃.It is 189℃lower than that without catalyst.A combination of structure and composition in the design of catalyst can be widely extended to other catalytic systems.  相似文献   

11.
A series of MnCeOx catalysts supported on cordierite honeycomb (Cord) were prepared by a combustion synthesis method using Mn(NO3)2 , Ce(NO3 )2·6H2O and citric acid. The effect of the molar ratio of Mn/Ce, calcination time, the amount of citric acid and the effect of water vapor on the catalytic properties for the complete oxidation of benzene were investigated. These catalysts were characterized by X-ray diffraction (XRD), H 2 temperature-programmed reduction (H2 -TPR), O2 temperature programmed desorption (O2 -TPD) and scanning electron microscopy (SEM) techniques. The results indicated that the MnCeOx /Cord catalyst with Mn/Ce molar ratio of 1:1, calcining for 7h and M n+ /(citric acid) molar ratio of 6 exhibited the highest catalytic activity. When the concentration of benzene was 1500 ppm and the gaseous hourly space velocity was 20000h -1 , the conversion of toluene was 99.1% at the reaction temperature of 300 oC.  相似文献   

12.
MnOx–CeO2 catalysts were synthesized to investigate the active sites for NO oxidation by varying the calcination temperature. XRD and TEM results showed that cubic CeO2 and amorphous MnOx existed in MnOx–CeO2 catalysts. High temperature calcination caused the sintering of amorphous MnOx and transforming to bulk crystalline Mn2O3. H2-TPR and XPS results suggested the valence of Mn in MnOx–CeO2 was higher than pure MnOx, and decreased with the increasing calcination temperature. The turnover frequency (TOF) was calculated based on the initial reducibility according to H2-TPR quantitation and kinetic study. The TOF results indicated that the initial reducibility of amorphous MnOx with high valence manganese ions was equivalent to the active sites for NO oxidation. It can be inferred that the amorphous MnOx plays a key role in low-temperature NO oxidation.  相似文献   

13.
MnOx(0.4)-CeO2 was investigated for soot oxidation assisted with a pulse dielectric barrier discharge(DBD).The catalysts were evaluated and characterized with TPO(temperature programmed oxidation),X-ray diffraction(XRD),Raman and X-ray photoelectron spectroscopy(XPS).The ignition temperature Ti for soot oxidation decreased from 240.8 to 216.4 oC with the increase of the pulse DBD frequencies from 50 to 400 Hz,lower than that of the case without pulse DBD present(253.4 oC).The results of XRD,Raman and XPS agreed well with the TPO activities of MnOx(0.4)-CeO2 towards soot oxidation.More solid solution of ceria and manganese,and surface reactive species including O2–,O– and Mn4+ were responsible for the enhancement of soot oxidation due to pulse DBD injection in the present study.For solid solution favors to the activation and transformation of those species,which are believed to be involved in the soot oxidation in a hybrid catalysis-plasma.  相似文献   

14.
A series of Lax K1–x CoO3 nanorod oxides with perovskite structure were synthesized by sol-gel method using polyvinyl alcohol(PVA) as additive.These perovskite-type complex oxide catalysts were characterized by the techniques of X-ray diffraction(XRD),infrared(IR),Brumauer-Emmett-Teller(BET) and scanning electron microscopy(SEM).And the results showed that nanorods of La1–x Kx CoO3 perovskite-type complex oxides were fabricated by sol-gel method when the mass concentration of PVA was 4% and the calcined temperature kept at 700 ℃ for 4 h.The catalytic results of CO oxidation showed that the Lax K1–x CoO3 catalysts had high activity.LaCoO3 nanorods exposed more {110} plane than LaCoO3 nanoparticles,which was beneficial to the catalytic oxidation of CO.LaCoO3 nanorods had the best catalytic performance for the oxidation of CO.At 200 oC,the CO conversion could reach 100%.  相似文献   

15.
Chemical interaction of Ce-Fe mixed oxides was investigated in methane selective oxidation via methane temperature programmed reduction and methane isothermal reaction tests over Ce-Fe oxygen carriers. In methane temperature programmed reduction test, Ce-Fe oxide behaved complete oxidation at the lower temperature and selective oxidation at higher temperatures. Ce-Fe mixed oxides with the Fe content in the range of 0.1–0.5 was able to produce syngas with high selectivity in high-temperature range(800–900 °C), and a higher Fe amount over 0.5 seemed to depress the CO formation. In isothermal reaction, complete oxidation occurred at beginning following with selective oxidation later. Ce1–xFexO2–δ oxygen carriers(x≤0.5) were proved to be suitable for the selective oxidation of methane. Ce-Fe mixed oxides had the well-pleasing reducibility with high oxygen releasing rate and CO selectivity due to the interaction between Ce and Fe species. Strong chemical interaction of Ce-Fe mixed oxides originated from both Fe*activated CeO2 and Ce3+ activated iron oxides(FeOm), and those chemical interaction greatly enhanced the oxygen mobility and selectivity.  相似文献   

16.
Various Er modified MnOx catalysts were synthesized using co-precipitation approach and tested in the selective catalytic reduction of NOx by ammonia(NH3-SCR).Catalysts were analyzed with various characterization techniques,and it is found that the doping of Er can enormously enhance the catalytic performance of MnOx catalyst.MnEr0.1 demonstrates advantageous catalytic performance in the NH3-SCR reaction owing to rich surface acidic sites,hi...  相似文献   

17.
Environmental contamination such as soot particles and NOx has aroused extensive attraction recently.However,the main challenge lies in the oxidation of soot at mild temperature with the assistance of NOx.Here,a series of core-shell MnCeOx catalysts were successfully synthesized by hydrothermal method and employed for low-temperature catalytic oxidation of soot in the presence of NOx.X-ray diffraction(XRD),inductively coupled plasma-optical emission sp...  相似文献   

18.
We documented(ⅰ) the decolorization of wastewater in visible light,which contains methyl orange,crystal violet and indigo carmine dyes,using La0.7Sr0.3Mn1-xFexO3(x=0.0,0.05,0.1 and 0.5) manganites and(ⅱ) efficient separation of photocatalysts from water using magnetic field.These ceramic photocatalysts were sintered at 1050℃ for 12 h.Ceramics were characterized by X-ray diffraction(XRD),soft X-ray absorption spectroscopy(SXAS),Fourier transf...  相似文献   

19.
In this study,Kx-Mn-Ce catalysts prepared by sol-gel method were investigated for toluene oxidation.Compared with Mn-Ce,the catalytic performance of Kx-Mn-Ce was further improved.X-ray diffraction(XRD),high resolution transmission electron microscopy(HRTEM) and Raman analyses demonstrate that K ions enter the lattice of CeO2 and disperse uniformly.The results of X-ray photoelectron spectroscopy(XPS),H2-temperature programmed reduction(H2-TPR...  相似文献   

20.
In the work, supported catalysts of FeOx and MnOx co-supported on aluminum-modified CeO2 was synthesized for low-temperature NH3-selective catalytic reduction (NH3-SCR) of NO. Impressively, the SCR activity of the obtained catalyst is markedly influenced by the adding amount of Al and the appropriate Ce/Al molar ratio is 1/2. The activity tests demonstrate that Fe–Mn/Ce1Al2 catalyst shows over 90% NO conversion at 75–250 °C and exhibits better SO2 resistance compared to Fe–Mn/CeO2. Fe–Mn/Ce1Al2 shows the expected physicochemical characters of the ideal catalyst including the larger surface and increased active reaction active sites by controlling the amount of Al doping. Also, the better catalytic activity is well correlated with the present advantaged surface adsorption oxygen species, Mn4+ species, Ce3+ species and the enhanced reducibility of Fe–Mn/Ce1Al2, which is superior to the Fe–Mn/CeO2 catalyst. More importantly, we further demonstrate that the amount and strength of surface acid sites are improved by Al-doping and more active intermediates (monodentate nitrate) is generated during NH3-SCR reaction. This work provides certain insight into the rational creation of simple and practical denitration catalyst environmental purification.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号