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1.
A series of MnMgAlO samples with different amounts of Ce doping were facilely prepared using coprecipitation method and their catalytic soot combustion activity was evaluated by temperature programmed oxidation reaction(TPO).The methods of X-ray diffraction(XRD),Brumauer-Emmett-Teller(BET),H2-TPR,NO-TPO and in situ IR were used to characterize the physiochemical properties of these samples.Dopant Ce improved the soot combustion performance of MnMgAlO catalyst due to the enhanced redox ability.Introduction of NOx led to the further increase of catalytic soot oxidation activity on these samples.Over Ce-containing samples,the catalytic activity was slightly decreased as the amount of dopant Ce increased in O2.Differently,in NO+O2,a certain amount of dopant Ce was much more favorable and excess amount of Ce resulted in a sharp drop of the catalytic soot combustion activity.Both NO2 and nitrates were found to have great contributions to the effects of NOx on the soot combustion activity of Ce-doped catalysts.More NO2 was generated as dopant Ce increased.When appropriate amount of Ce was introduced,the as-formed NO2 was stored as bridging bidentate nitrate on Mn-Ce site,which was confirmed to have higher reactivity with soot than nitrite or monodentate nitrate on Mn and/or Ce sites.Overall,Mn0.5Mg2.5Ce0.1Al0.9O was considered as the most potential catalyst for soot combustion.  相似文献   

2.
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   

3.
Mesoporous CeMnOx composite oxides catalysts were prepared by surfactant-assisted co-precipitation method and used for the catalytic oxidation of toluene.The effect of different cerium precursors[Ce(NO_3)_3 and(NH_4)_2 Ce(NO_3)_6] on catalyst structure,surface properties and toluene combustion activities of mesoporous CeMnO_x catalysts were investigated.The Ce(Ⅲ)MnO_x catalyst prepared from Ce(NO_3)_3 precursor shows higher catalytic activity,with a 90% conversion temperature of 240℃,which is better than the Ce(Ⅳ)MnO_x catalyst derived from(NH_4)_2 Ce(NO_3)_6] precursor.On the basis of characterizations,it reveals that abundant surface content of Mn~(4+),better redox behavior and larger concentration of surface active oxygen species are responsible for the excellent catalytic performance.  相似文献   

4.
Constructing cerium and manganese bimetallic catalysts with excellent catalytic performance for soot combustion is the research frontier at present. In order to find out the key factors for catalytic soot combustion of Ce–Mn–O catalysts, a series of Ce–Mn–O catalysts with different Ce/Mn proportions were prepared by co-precipitation method. The activity test results show that it increases first and then decreases with the increase of Mn content. The best catalytic activity is obtained for Ce0.64Mn0.36 catalyst, which shows a maximum rate temperature (Tm) at 306 °C for CO2 production in TPO curve. Compared with non-catalytic soot combustion, the Tm decreases by more than 270 °C. Systematical characterization results suggest that when the adsorbed surface oxygen, lattice oxygen, specific surface area and total reduction amount of the catalysts reach a certain value, the key factors leading to the difference of catalytic activity become the readily reducible and highly dispersed surface manganese oxide species and contact performance of the external surface. The surface manganese oxide species is beneficial to improving the low-temperature reducibility of catalysts and the porous surface is conducive to the contact between catalyst and soot. Furthermore, for the soot combustion reaction containing only O2, the promoting effect of Mn4+ is not obvious.  相似文献   

5.
A series of Ce1–xTixO2 mixed oxide catalysts were synthesized by sol-gel method and then loading of noble metal (M = Pt, Rh, Ru) was used for soot oxidation. Ti-doped Ce1–xTixO2 catalysts (x is the molar ratio of Ti/(Ti + Ce) and ranges from 0.1 to 0.5) exhibit much better oxidation performance than CeO2 catalyst, and the Ce0.9Ti0.1O2 catalyst calcined at 500 °C has the best catalysis activity. Each noble metal (1 wt%) was supported on Ce0.9Ti0.1O2 (M/C9T1) and the properties of the catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman, Brunauer–Emmett–Teller (BET) method, and H2-temperature programmed reduction (H2-TPR) results. Results show that the introduction of Ti into CeO2 forming Ti-O-Ce structure enhances the catalytic activity and increases the number of oxygen vacancies at the catalyst surface. The noble metal is highly dispersed over Ce0.9Ti0.1O2, and M/C9T1 catalysts present enhanced activity in comparison to Ce0.9Ti0.1O2. It is found that noble metals can greatly increase the activity of the catalyst and the corresponding oxidation rate of soot can enhance the electron transfer capacity and oxygen adsorption capacity of the catalyst. A small amount of Ti doping in CeO2 can significantly improve the activity of the catalyst, while a large amount of Ti reduces the performance of the catalyst because a large amount of Ti is enriched on the surface of the catalyst, which hinders the contact and reaction between the catalyst and the soot.  相似文献   

6.
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   

7.
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   

8.
Low-temperature selective catalytic reduction (SCR) is important for the elimination of NOx from stationary sources. In the present study, the loading of Ce and W on α-Fe2O3 was achieved through the integration of single-mode microwave and incipient wetness impregnation (IWI) methods. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images reveal that the structure of α-Fe2O3 is spindle-like, and the structure remains unchanged after the introduction of Ce and/or W. The results of NH3-SCR investigation demonstrate that NOx conversion over Ce–W/α-Fe2O3 is more than 85% at 300 °C, which is much higher than that over Ce/α-Fe2O3 and α-Fe2O3. Our studies illustrate that the addition of Ce can significantly increase the amount of surface oxygen vacancies as well as sites of moderate basicity. On the other hand, the addition of W can obviously decrease the amount of basic sites and increase the number of Brønsted acid sites. The synergistic effect of Ce and W addition on balancing acidity/basicity properties accounts for the high activity of Ce20W10/α-Fe2O3 for NOx removal at low temperatures. The study provides insight into the relationship between acidity/basicity properties and catalytic performance of Ce–W/α-Fe2O3 catalysts, which is beneficial to the design of high-performance NH3-SCR catalyst for NOx removal at low temperatures.  相似文献   

9.
A series of Ba/CeO2 catalysts with different Ba loading amounts were prepared by incipient wetness impregnation. Their NOx adsorption behaviors under NO and NO+O2 conditions were investigated by in situ DRIFTS. It was found that NOx was ad-sorbed and stored in the form of nitrites and nitrates on both Ba and Ce sites on the surface of the catalysts. The less thermally stable BaCO3 was suggested to be the main active phase for NOx trapping. Ceria served primarily as an oxygen supplier in the absence of O2, and the reaction from nitrites to nitrates on Ba sites was the key step in this case. In the presence of O2, however, gaseous O2 became the main oxygen source. The NOx adsorption capacity of the catalyst was dominated by the Ba content. Moreover, the stability of ni-trites and nitrates formed on Ce sites was found to be lower than those formed on Ba sites which existed in the form of the ionic bar-ium nitrate species.  相似文献   

10.
The CeO2, Ce–Nb–Ox and Nb2O5 catalysts were synthesized by citric acid method and the promotion effect of Nb on ceria for selective catalytic reduction (SCR) of NO with NH3 was investigated. The catalytic activity measurements indicate that the mixed oxide Ce–Nb–Ox presents a higher SCR activity than the single oxide CeO2 or Nb2O5 catalyst. In addition, the Ce–Nb–Ox catalyst shows high resistance towards H2O and SO2 at 280 °C. The Raman, X-ray photoelectron spectra and temperature programmed reduction with H2 results indicate that the incorporation of Nb provides abundant oxygen vacancies for capturing more surface adsorbed oxygen, which provides a superior redox capability and accelerates the renewal of active sites. Furthermore, the Fourier transform infrared spectra and temperature programmed desorption of NH3 results suggest that niobium pentoxide shows high surface acidity, which is partly retained in the Ce–Nb–Ox catalyst possessing a high content of Lewis and Brønsted acid sites. Therefore, the incorporation of Nb improves both the redox and acidic capacities of Ce–Nb–Ox catalyst for the SCR reaction. Here, the redox behavior is primarily taken on Ce and the acidity is well improved by Nb, so the synergistic effect should exist between Ce and Nb. In terms of the reaction mechanism, in situ DRIFT experiments suggest that both NH3 on Lewis acid sites and NH4+ on Brønsted acid sites can react with NO species, and adsorbed NO and NO2 species can both be reduced by NH3. In the SCR process, O2 primarily acts as the accelerant to improve the redox and acid cycles and plays an important role. This work proves that the combination of redox and acidic properties of different constituents can be feasible for catalyst design to obtain a superior SCR performance.  相似文献   

11.
Three dimensionally ordered macroporous(3 DOM) Ce-based catalysts were successfully prepared via a surfactant-assisted colloidal crystal template(CCT) route. The as-synthesized catalysts showed wellordered structures with macropores and small interconnected pore windows. The Raman results indicate that the catalyst persists pure fluorite cubic phases until the molar ratio of Mn exceeds 0.3, therefore MnO_x particles form and impede the contact of the active site and the reagent and restraining soot combustion. The doping of Nd into MnO_x-CeO_2 enhances the catalytic activity because of increased oxygen vacancy, Mn~(4+)content and stronger redox ability. Nd-doping also improves thermal stability of the catalyst due to less sintering and none phase separation after thermal aging. The fresh and aged Mn_(0.3)Ce_(0.6)Nd_(0.1)O_2 catalysts show the maximum oxidation rate for soot at 331 and 355 ℃ in the O_2/N_2 atmosphere, achieving a nearly 100% CO_2 selectivity.  相似文献   

12.
The effect of manganese and/or ceria loading of V_2 O_5-Mo_O_3/TiO_2 catalysts was investigated for selective catalytic reduction(SCR) of NO_x by NH_3.The manganese and/or ceria loaded V_2 O_5-MoO_3/TiO_2 catalysts we re prepared by the wetness impregnation method.The physicochemical characteristics of the catalysts were thoroughly characterized.The catalytic performance of 1.5 wt% V_2 O_5-3 wt% MoO_3/TiO_2(V1.5 Mo3/Ti) is greatly enhanced by addition of 2.5 wt% MnO_x and 3.0 wt% CeO_2(V1.5 Mo3 Mn2.5 Ce3/Ti) below450℃.Compared with the V1.5 Mo3/Ti catalyst with NO_x conversion of 75% at 275 ℃,V1.5 Mo3 Mn2.5 Ce3/Ti exhibits higher NO_x conversion of 84% with good resistance to SO_2 and H_2 O at a gas hourly space velocity value of 150000 h~(-1).The active manganese,cerium,molybdenum,and vanadium oxide species are highly dispersed on the catalyst surface and some synergistic effects exist among these species.Addition of MnO_x significantly enhances the redox ability of the cerium,vanadium,and molybdenum species.Addition of Ce increases the acidity of the catalyst.More active oxygen species,including surface chemisorbed oxygen,form with addition of Mn and/or Ce.Because of the synergistic effects,appropriate proportions of manganese in different valence states exist in the catalysts.In summary,the good redox ability and the strong acidity contribute to the high NH3-SCR activity and N2 selectivity of the V1.5 Mo3 Mn2.5 Ce3/Ti catalyst in a wide temperature range.And the V1.5 Mo3 Mn2.5 Ce3/Ti catalyst shows good resistance to H_2 O and SO2 in long-time catalytic testing,which can be ascribed to the highly sulfated species adsorbed on the catalyst.  相似文献   

13.
The activity and hydrothermal stability of the Rh/Ce_xZr_(1-x)O_2(x=0,0.05,0.3,0.5) model three-way catalysts for gasoline vehicle emissions control were investigated in this work.Among the Rh/Ce_xZr_(1-)_xO_2 samples with different Ce/Zr ratios,the Rh/ZrO_2 sample exhibits a significantly better activity and hydrothermal stability than the rest of the samples.The impacts of having more Ce components in the Rh/Ce_xZr_(1-x)O_2 catalysts are associated with the strong Rh-O-Ce interaction that tends to over stabilize the rhodium species.A significant amount of such rhodium atoms can be found in the bulk of the support oxides after a hydrothermal aging at 1050℃ with 10% H_2 O in air for 12 h.Differently,the sintering of rhodium on the surface of Rh/ZrO_2 catalysts is the main reason for the catalyst deactivation during the hydrothermal aging.These findings provide an example where high dispersion of supported metal induced by strong metal-support interactions does not necessarily lead to high catalytic activity.  相似文献   

14.
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   

15.
In this paper, CuOx@Ag/CeO2 catalysts were synthesized by simple wet-chemical method and equal volume impregnation method. The obtained catalysts were subjected to soot temperature programmed oxidation (soot-TPO) activity tests and were further characterized by various techniques such as X-ray diffraction (XRD), transmission electron microscopy/high-resolution transmission electron microscopy (TEM/HR-TEM), N2 physisorption, X-ray photoelectron spectroscopy (XPS) and H2-temperature programmed reduction (H2-TPR). The results show that CuOx@Ag/CeO2 synthesized presents well controlled core-shell structures, with nano-cube like Cu2O as the core and Ag decorated polycrystalline CeO2 grafting layers as the shell. Such core-shell structured CuOx@Ag/CeO2 can successfully construct a secondary oxygen delivery channel (CuOx → CeO2 → Ag) to effectively transfer bulk oxygen of the catalyst to the soot, resulting in its excellent soot oxidation activity compared to CuOx@CeO2. The potential benefiting effect by Ag introduction over Cu@Ag/Ce can be concluded as: (i) pumping lattice oxygen and accelerating gaseous O2 dissociation to generate significantly increased active surface oxygen content; (ii) modulating a moderate surface oxygen vacancies concentration to maintain more highly active O2 species.  相似文献   

16.
In this work, V/Ce–Ti catalysts were modified with different kinds of transition metals (Cu, Fe, Co, Mn) by sol–gel and impregnation methods. The NH3 oxidation performance of them was tested to select the most active catalyst in NH3-selective catalytic oxidation (NH3–SCO). The effect of NO, SO2 and H2O was also investigated. The experimental results indicate that 1% Cu–V/Ce–Ti catalyst exhibits the most significant ability to remove slip ammonia discharged from coal-fired plants and its NH3 conversion efficiency reaches 90% at 300 °C. In addition, 97% NOx can be removed when NO is introduced in the gas. Cu–V/Ce–Ti catalyst also obtains good resistance to H2O and SO2. Based on the characterization experiment, the introduced Cu and V are highly dispersed on Ce–Ti catalyst and they can increase the redox properties and the number of acidic sites. Besides, the redox cycles among Cu, V and Ce species on Cu–V/Ce–Ti catalyst surface are conducive to generating more active oxygen and promoting the oxidation capacity of the catalyst.  相似文献   

17.
SAPO-34,SAPO-5/34 based catalysts doped with Cu,Ce as active components were synthesized via a one-pot hydrothermal method by using different amounts of additive(a-cellulose),and their catalytic activities were measured for selective catalytic reduction(SCR) of NO with NH3.The synthesized Cu-Ce co-doped products switch from cubic SAPO-34,to flower-like aggregated SAPO-5/34,hybrid crystal SAPO-5/34,and finally to spherical aggregated SAPO-34 with the increase of α-cellulose amount.The Cu-Ce co-doped SAPO-5/34 hybrid crystal structure catalysts with 0.75 mol ratios of C/P(Cu-Ce/SP-0.75)exhibit excellent NH3-SCR activity with higher than 90% NO_x conversion in the temperature range of 180-450℃,at WHSV of 20000 mL/(g·h).Furthermore,the catalyst displays outstanding sulfur resistance and NO_X conversion maintains above 90% at 200-450℃ after adding 100 ppm of SO_2.The characteristic results suggest that the high deNO_X performance of Cu-Ce/SP-0.75 is due to the enhanced accessibility,abundant activity species,excellent redox property and high adsorptive and activated capacity for NH3.  相似文献   

18.
Due to strong synergistic effect of the elements,a series of XEuMnOx ternary oxides(X=Ce,Ni,Co,Sb,Sn,Mo) were synthesized by one-pot co-precipitation method,and composite components were identified and optimized to maintain high activity and superior SO2 and H2O endurance in selective catalytic reduction of NOx with NH3(NH3-SCR).NOx conversion of CeEuMnOx ternary oxide catalysts attains more than 90% at 100-2...  相似文献   

19.
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   

20.
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   

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