Effect of synthesis methods on activity of V_2O_5/CeO_2/WO_3-TiO_2 catalyst for selective catalytic reduction of NO_x with NH_3

The effect of synthesis methods on the activity of V/Ce/WTi catalysts was investigated for the selective catalytic reduction(SCR) of NO_x by NH_3. V/Ce/WTi-DP(deposition precipitation) catalyst showed excellent NH_3-SCR performance, especially the better medium-temperature activity and the less N_2O formation than V/Ce/WTi-IMP(impregnation). These catalysts were characterized by X-ray diffraction(XRD), Brumauer-Emmett-Teller(BET), X-ray photoelectron spectroscopy(XPS), temperature-programmed reduction(H_2-TPR), and in situ DRIFTS techniques. The XPS and H_2-TPR results revealed that V/Ce/WTi-DP exhibited more surface Ce species, higher level of Oα and higher reducibility of Ce species. Reflected by in situ DRIFTS results, the deposition precipitation method(DP) contributed to a greater amount of weakly adsorbed NO_2, monodentate nitrate and NH_3 species with better reactive activity. Meanwhile, the cis-N_2O_2~(2–) species, an intermediate for N_2O formation, was very limited. As a result, these advantages brought about the superior SCR activity and N_2 selectivity for V/Ce/WTi-DP.     

Rare earth containing catalysts for selective catalytic reduction of NO_x with ammonia:A Review

Increasingly stringent regulations in many countries require effective reduction and control of NOx emissions. To meet these limits, various methods have been exploited, among which the selective catalytic reduction of NOx using ammonia as the reductant(NH3-SCR) is the most favored technology. High catalytic activity, N2 selectivity and resistance to deactivation by sulfur, alkaline metals and hydrothermal conditions are the optimal properties of a successful SCR catalyst. Rare earth oxides, particularly CeO2, have been increasingly used to improve the catalytic activity and resistance to deactivation of deNOx catalysts, both modifying traditional vanadium catalysts, and also developing novel catalysts, especially for low temperature applications. This review summarized the open literature concerning recent research and development progresses in the application of rare earths for NH3-SCR of NOx. Additionally, the roles of rare earths in enhancing the performance of NH3-SCR catalyst were reviewed.     

In-situ DRIFT assessment on strengthening effect of cerium over FeO_x/TiO_2 catalyst for selective catalytic reduction of NO_x with NH_3

Fe-based catalysts have a great potential to be used for selective catalytic reduction(SCR) of NO_x with NH3 reaction due to their low cost,nontoxicity and excellent catalytic activity.The aim of this paper is to investigate Ce doping effect on activity of NH_3-SCR over the FeO_x/TiO_2 catalyst.In-situ diffuse reflectance infrared fourier transform(DRIFT) technology was utilized to verity the adsorbed species on the surface of FeO_x/TiO_2 and FeO_x-CeO_2/TiO_2 catalysts.With respect to the obtained results,among the four catalysts studied,the FeO_x-CeO_2/TiO_2 with the FeO_x/CeO_2 ratio of 3/8 shows the best NO conversion more than 98%in the temperature range of 230—350℃,The active centers for NH_3 adsorption and activation are assigned to Lewis acid sites over the FeO_x-CeO_2/TiO_2 and monodentate nitrates can act as the key intermediate in the NH3-SCR.Moreover,both of Langmuir-Hinshelwood and Eley-Rideal mechanisms are observed over the FeO_x-CeO_2/TiO_2 catalysts in the SCR.     

Promoting effect of microwave irradiation on CeO_2-TiO_2 catalyst for selective catalytic reduction of NO by NH_3

In this work we prepared several CeO₂-TiO₂ catalysts for the NH₃-SCR reactionusing co-precipitation with assistance of microwave irradiation. The catalytic NH₃-SCR activities over CeO₂-TiO₂ catalysts at low temperatures are largely enhanced by the treatment of microwave irradiation, the operation temperature window is also broadened. For better understanding the promotion mechanism, the catalyst prepared by conventional co-precipitation with and without microwave irradiation treatment was characterized with H₂-TPR, NH₃-TPD, XPS, XRD and BET. Microwave irradiation treatment accelerates the crystallite rate of CeO₂-TiO₂ catalysts, and greatly enlarges their surface area by adjusting their microstructures. The resistance to SO₂ and H₂O is also improved via regulating the hierarchical pore structure by the microwave irradiation. Microwave irradiation treatment can also improve the redox property and increase the acid sites over the catalyst surfaces. The result of in situ DRIFTS suggests that the microwave irradiation treatment generates more Brønsted acid sites on CeO₂-TiO₂-2 h catalyst, helpful in SCR reactions. XPS results show that after microwave irradiation on the CeO₂-TiO₂ catalysts, the surface demonstrates an elevated concentration of chemisorbed oxygen, consequently leading to better oxidation of NO to NO₂. Additionally, the molar ratio of Ce³⁺/Ce⁴⁺ has been elevated after being treated by microwave irradiation, a vital factor in enhancing the NH₃-SCR activities.     

New insights into the role of vanadia species as active sites for selective catalytic reduction of NO with ammonia over VO_x/CeO_2 catalysts

A series of VO_x/CeO_2 catalysts we re synthesized via vanadia supported on ceria with different BET surface areas.The catalysts were employed to investigate the active sites for the selective catalytic reduction of NO with NH_3(NH3-SCR).The kinetic results show that VO_x/CeO_2 catalysts exhibit nearly constant apparent activation energies(E_a),indicating the same SCR reaction mechanism.The V-O-Ce bridging modes and oligomeric VO_x were identified and quantified by Raman,FT-IR and H_2-TPR.The amounts of the V-O-Ce bridging modes calculated by H_2-TPR are correlated to the NH_3-SCR intrinsic reaction rates.The turnover frequencies(TOFs) show a constant value at the same temperature,which were calculated based on the number of V-O-Ce bridging modes of VO_x/CeO_2 catalysts.Therefore,it can be concluded that the V-O-Ce bridging modes are the active sites of VO_x/CeO_2 catalysts for the NH3-SCR reaction.     

Hydrothermal and sulfur aging of CeTi/CeWTi catalysts for selective catalytic reduction of NO_x with NH_3

The CeO_2-TiO_2(CeTi)and CeO_2/WO_3-TiO_2(CeWTi)catalysts were prepared by sol-gel method.The asprepared catalysts were hydrothermally treated at 760 ℃ for 48 h in air containing 10 vol% H_2O to obtain the hydrothermal aged catalysts.The sulfur aged catalysts were treated at 400 ℃ with 100 ppm SO_2,10%water vapor,air balance for 48 h and catalysts.The powder X-ray diffraction(XRD)and Raman results indicate that the crystallization of hydrothermal aged catalysts is more serious than sulfur aged catalysts.In addition,tungsten species can stabilize the CeTi catalyst from grain growth.According to the results of in situ diffuse reflectance infrared Fourier transform spectra(DRIFTS),temperatureprogrammed desorption of ammonia(NH_3-TPD),H_2 temperature-programmed reduction(H_2-TPR)and ammonia oxidation,the aging process leads to loss of surface area,redox properties,surface acidities and surface ceria concentration,especially for the hyd rothermal aging.The NH_3-NO/NO_2 SCR perfo rmances of sulfur aged catalysts are better than that of hydrothermal aged catalysts.Compared with CeTi catalyst,the addition of tungsten inhibits the crystallization of catalyst.So that more acid sites and active sites are retained.This is also the reason why tungsten addition improves the NH_3-NO/NO_2 SCR performance of CeTi catalyst.     

Effect of Ce doping into V_2O_5-WO_3/TiO_2 catalysts on the selective catalytic reduction of NO_x by NH_3

In this work, the effectiveness of V_2O_5-WO_3/TiO_2 catalysts modified with different CeO_2 contents by impregnation and co-precipitation methods on the selective catalytic reduction of NOxby NH3 have been studied comparatively by various experimental techniques. The results showed that the NO conversion of V_2O_5-WO_3/CeO_2-TiO_2 catalysts modified by co-precipitation method obviously increased with the Ce doping contents in the studied range below 20%(All Ce contents are in mass fractions), but the NO conversion of V_2O_5-WO_3/CeO_2/TiO_2 catalysts modified by impregnation methods was lower than V_2O_5-WO_3/CeO_2-TiO_2 catalysts especially beyond 2.5% Ce doping contents. The V_2O_5-WO_3/CeO_2-TiO_2 catalysts showed better SCR activity, wider reaction window, and higher sulfur and water resistance. The characterization results elucidated that the modified catalysts by co-precipitation method exhibited higher specific surface area, much better dispersity of Ce component, more Ce~(3+)species and more Br?nsted acid sites than that by impregnation. The vacancies caused by more Ce~(3+)species were favorable for more NO oxidation to NO_2, and the interaction between Ce species and WOxspecies generated more Br?nsted acid sites. It could be supposed that dispersed Ce Oxspecies and WOxspecies offered more second active centers respectively to adsorb oxygen and activate ammonia as co-catalysis to the primary active center of V ions, thus facilitated the better SCR activity of modified V_2O_5-WO_3/CeO_2-TiO_2 catalysts by coprecipitation methods. The co-precipitation methods with Ce component were more suitable for production of modified commercial V_2O_5-WO_3/TiO_2 catalysts.     

Effect of pore-size distribution on Ru/ZSM-5 catalyst for enhanced N_2 activation to ammonia via dissociative mechanism

In the present study,a series of Ru/ZSM-5 catalysts with different pore-size distributions were prepared and investigated for NH_3 synthesis.Our studies indicate that Ru/ZSM-5-Mic with micropore structure exhibits superior NH_3 synthesis rate,which is much higher than those of Ru/ZSM-5-Mac(with macroporous structure) and Ru/ZSM-5-Mes(with mesoporous structure) catalysts.A series of TPD experiments demonstrate that pore-size distributions play an important role in N_2 adsorption and activation over Ru/ZSM-5.Moreover,the addition of La significantly promotes the NH_3 synthesis performance over Ru/ZSM-5-Mic.Additionally,in situ DRIFTS studies indicate that the main intermediate species over Ru/ZSM-5-Mic are-NH_2,and most of the surface hydrogen species desorb following the H_2O-formation pathway.     

Effect of manganese and/or ceria loading on V_2O_5-MoO_3/TiO_2 NH_3 selective catalytic reduction catalyst

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.     

Effect of praseodymium additive on CeO_2(ZrO_2)/TiO_2 for selective catalytic reduction of NO by NH_3

A series of praseodymium added CeO_2(ZrO_2)/TiO_2 catalysts separately prepared by methods of sol-gel and impregnation were tested for selective catalytic reduction of NO, and characterized by X-ray diffraction(XRD), N_2-brumauer-emmett-teller(N_2-BET), NH_3-temperature programmed desorption(NH_3-TPD), H_2-temperature programmed reduction(H_2-TPR), PL spectra, Raman spectra, electron paramagnetic resonance(EPR) and X-ray photoelectron spectroscopy(XPS), respectively. Influence of preparation method on catalytic performance was studied. Results showed that the influence of Pr addition on catalytic performance of the CeO_2(ZrO_2)/TiO_2 catalysts was different between the sol-gel method and the impregnation method. The Pr addition tended to interact with TiO_2 and formed the structure of Ti-O-Pr in the sol-gel method while it was more likely to interact with CeO_2 forming the structure of Ce-O-Pr in the impregnation method. The total acid amount and redox properties of the catalysts prepared by sol-gel method decreased with the addition of Pr element, which resulted in decrease of catalytic activity. In contrast, the Pr-added catalyst prepared by impregnation method was found to possess easier reducibility, more total acid amount and higher proportion of Ce~(3+) species, which was favourable for higher catalytic activity.     

Promotion effect of niobium on ceria catalyst for selective catalytic reduction of NO with NH3

The CeO₂, Ce–Nb–O_x 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–O_x presents a higher SCR activity than the single oxide CeO₂ or Nb₂O₅ catalyst. In addition, the Ce–Nb–O_x 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–O_x 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–O_x 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.     

Revealing active species of CePO4 catalyst for selective catalytic reduction of NOx with NH3

Revealing the active species of the catalyst is conducive to the design of more efficient catalyst.Herein,we tried to demonstrate the roles of amorphous and crystalline structures on CePO₄ catalyst during selective catalytic reduction(SCR) of NO_x by NH₃.Higher calcination temperature promotes the transfer of amorphous structure to crystalline structure on the surface of CePO₄.Both amorphous and crystalline CePO₄ species on CePO-X samples can...     

Influence of CePO4 with different crystalline phase on selective catalytic reduction of NOx with ammonia

A series of cerium phosphate catalysts with different crystal phases were synthesized by hydrothermal method and co-precipitation method.Hexagonal cerium phosphate(CePO₄-H) shows better NH₃-SCR denitration activity than monoclinic cerium phosphate(CePO₄-M) and mixed phases of CePO₄-H and CePO₄-M.Moreover,CePO₄-H also exhibits excellent activity stability with stream time and cycling stability.Various characterizations were carried...     

Effects of PbO poisoning on Ce-Mn/AC catalyst for low-temperature selective catalytic reduction of NO with NH3

As a common heavy metal in the sintering flue gas,Pb can exist in the form of oxide(PbO)and lead to the decrease in the denitration catalysts activity.Ce-Mn/AC(activated carbon)and PbO-Ce-Mn/AC catalysts were prepared by impregnation method and their selective catalytic reduction of NH₃ with NO was studied.Results showed that selective catalytic reduction activity of Ce-Mn/AC decreased remarkably after doping PbO.And the NO conversion of Ce-Mn/AC reached 94.52% at 200℃,while the value was reduced to 65.8% after doping PbO at the same temperature.The doping of PbO decreased the total pore volume and oxygen functional groups of activated carbon,increased crystallinity of Mn oxides on the catalyst,decreased Mn⁴⁺ and chemisorbed oxygen content and then inhibited the“fast selective catalytic reduction”denitration reaction for Ce-Mn/AC catalysts.On this basis,the poisoning effects of lead oxide on Ce-Mn/AC catalysts for low-temperature selective catalytic reduction were revealed.     

Effects of water on CO catalytic oxidation over Pd/CeO_2

The role of water in CO oxidation was investigated on Pd/CeO_2 with different morphologies(rods(R),cubes(C) and octahedrons(O)).Compared with the absence of water,CO oxidation activity increases 2 times in the presence of water on Pd/CeO_2-C;but a decrease is found on Pd/CeO_2-R.Catalyst characterization reveals that Pd is mainly in the form of solid solution(Pd_xCe_(1-x)O_(2-σ)) on Pd/CeO_2-R and a mixture of metal and Pd_xCe_(1-x)O_(2-σ) solid solution on Pd/CeO_2-C.The strong interaction between Pd and CeO_2-R results in the form of stable bidentate carbonates species;while the relatively weak interaction between Pd and CeO_2-C leads to the produce of unstable monodentate carbonates species.The effects of water on CO oxidation activity closely relate with the Pd chemical state and the types of carbonates species.Water restrains CO adsorption on Pd_xCe_(1-x)O_(2-σ) solid solution,but it has negligent effects on metallic Pd species.In the presence of water,bidentate carbonates species remains stable but the decrease in the amount of monodentate carbonates species is observed.     

A novel catalyst of silicon cerium complex oxides for selective catalytic reduction of NO by NH3

A series of CeO2/SiO2 and SixCe1-xO2 complex oxides supported on an activated Al2TiO5-TiO2-SiO2 complex phase (ATS) ceramics were prepared by step impregnation and co-impregnation methods, and characterized by N2-BET, XRD, SEM and NH3-TPD techniques. The effects of reaction temperature, CeO2/SiO2 loadings and Si/Ce molar ratio on the granular catalysts for NO selective catalytic reduction with ammonia (NH3-SCR) were studied. Results indicated that both CeO2/SiO2/ATS and CeO2/ATS catalysts showed the same ac...     

Influence of CeO_2 loading on structure and catalytic activity for NH_3-SCR over TiO_2-supported CeO_2

A series of supported CeO_2/TiO_2 catalysts were prepared to explore the influence of CeO_2 loading on these catalysts for the selective catalytic reduction of NO_3 by NH_3(NH_3-SCR).The catalysts were investigated in detail by means of XRD,Raman,H_2-TPR,NH_3-TPD,XPS,in situ DRIFTS,and NH3-SCR reaction.The activity of the catalyst is closely related to the content of CeO_2.When the loading of CeO_2 is near the dispersion capacity(1.16 mmol Ce~(4+)/100 m~2 TiO_2),the catalytic activity is better.This may be because that the dispersed CeO_2 is the active species and the catalyst has appropriate redox property,along with the larger amounts of surface Ce content and surface adsorbed oxygen species.Finally,a possible reaction mechanism via the Langmuir-Hinshelwood(L-H) mechanism is tentatively proposed to further understand the NH_3-SCR reaction.     

Promotional effect of CO pretreatment on CuO/CeO2 catalyst for catalytic reduction of NO by CO

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.     

A-site defects in LaSrMnO_3 perovskite-based catalyst promoting NO_x storage and reduction for lean-burn exhausts

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.     

Effect of Na+on catalytic performance of CoCe/ZSM-5 catalysts for oxidation of toluene

A CoCe/ZSM-5 catalyst was prepared by ultrasonic-assisted impregnation for the catalytic combustion of toluene.To study the effect of Na+on catalytic performance of CoCe/ZSM-5 catalysts,a series of different Si/Al ZSM-5 zeolites and catalysts doped with Na were synthesized.The experimental results show that 0.71 wt%Na+can inhibit active growth,generate more active small crystal grains,and promote improvement of the catalytic activity by the grain boundary segregation block mechanism,and the catalyst with 0.71 wt%of Na shows toluene conversion of 90 vol%at 250℃.Over 0.71 wt%of Na+content will neutralize the acid centre of the catalyst,lowering the specific surface area of the catalyst and resulting in a gradual decrease in the catalytic activity.