A highly active VOx-MnOx/CeO2 for selective catalytic reduction of NO: The balance between redox property and surface acidity

Excellent catalysts with low-temperature activity and relatively wide temperature window for selective catalytic reduction of NO with ammonia (NH₃-SCR) are highly demanded in view of the practical treatment of NO. Herein, we have designed a highly active VO_x-MnO_x/CeO₂ material based on the intrinsic requirement of SCR reaction for catalyst, namely redox sites and surface acid sites. The vanadium oxide and manganese oxide are highly dispersed over the ceria mesosphere via simple incipient wetness impregnation. The loading of manganese could introduce acid sites and enhance the redox property remarkably, while the loading of vanadium increases acid sites and weakens redox property. Through tentatively controlling the appropriate loading ratio of the two components, the optimal catalyst achieves a balance between redox property and surface acidity. The work shed light on the development of new SCR catalyst with superior low temperature activity, wide work temperature window and good hydrothermal stability.     

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.     

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.     

Sm-MnOx catalysts for low-temperature selective catalytic reduction of NOx with NH3: Effect of precipitation agent

A series of Sm-Mn mixed oxide catalysts were prepared via precipitation using various precipitants,namely Na₂CO₃(NH₄)₂CO₃,and NH₃·H₂O,and evaluated for the selective catalytic reduction(SCR) of NO_x with NH₃ at low temperatures.Various characterisation techniques were used to determine the physicochemical properties of the catalysts,and it is found that their catalytic performance is greatly influen...     

Promoting effect and mechanism of neodymium on low-temperature selective catalytic reduction with NH3 over Mn/TiO2 catalysts

Series of Mn/TiO₂ catalysts modified with various contents of Nd for low-temperature SCR were synthesized. It can be found that the appropriate amount of Nd can markedly reduce the take-off temperature of Mn/TiO₂ catalyst to 80 °C and NO_x conversion is stabilized over 90% in the wide temperature range of 100–260 °C. 0.1Nd–Mn/Ti shows higher N₂ selectivity and better SO₂ resistance than Mn/Ti catalyst. The results reveal that Nd-doped Mn/TiO₂ catalyst exhibits larger BET surface area and better dispersion of active component Mn₂O₃. XPS results indicate that the optimal 0.1Nd–Mn/Ti sample possesses higher concentration of Mn⁴⁺ and larger amount of adsorbed oxygen at the surface compared with the unmodified counterpart. In situ DRIFTS show that the surface acidity is evidently increased after adding Nd, especially, the Lewis acid sites, and the intermediate (-NH₂) is more stable. The reaction mechanism over Mn/Ti and 0.1Nd–Mn/Ti catalysts obey the Eley-Rideal (E-R) mechanisms under low temperature reaction conditions. H₂-TPR results show that Nd–Mn/TiO₂ catalyst exhibits better low-temperature redox properties.     

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.     

Er-modified MnOx for selective catalytic reduction of NOx with NH3 at low temperature: Promoting effect of erbium on catalytic performance

Various Er modified MnO_x catalysts were synthesized using co-precipitation approach and tested in the selective catalytic reduction of NO_x 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.MnEr_0.1 demonstrates advantageous catalytic performance in the NH₃-SCR reaction owing to rich surface acidic sites,hi...     

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.     

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.     

Low-temperature NH_3-SCR of NO_x over MnCeO_x/TiO_2 catalyst:Enhanced activity and SO_2 tolerance by modifying TiO_2 with Al_2O_3

A series of TiO_2-Al_2 O_3 composites with Al/Ti molar ratios of 0.1,0.2,and 0.4 were synthesized by a coprecipitation method and used as supports to prepare supported MnCeO_x catalysts by an impregnation method.The physico-chemical properties of the samples were extensively characterized by N2 physisorption,X-ray diffraction,Raman spectroscopy,scanning electron micro scopy and energy-dispersive Xray spectroscopy element mapping,X-ray photoelectron spectroscopy,H_2-temperature programmed reduction,ammonia temperature programmed desorption,and in-situ diffuse reflectance infrared Fourier transform spectroscopy.The catalytic activity and resistance to water vapor and SO_2 of the asprepared catalysts for the SCR of NO_x with NH3 were evaluated at 50-250℃ and GHSV of 80000 mL/(g_(cat)·h).The results reveal that MnCeO_x/TiO_2-Al_2 O_3 exhibits higher activity and better SO2 tolerance than MnCeO_x/TiO_2.Combining with the characterization results,the enhanced activity and SO2 tolerance of MnCeO_x/TiO_2-Al_2 O_3 can be mainly attributed to higher relative concentrations of Mn~(4+)and chemisorbed oxygen species,stronger reducibility,and larger adsorption capacity for NH3 and NO,which originate from the larger specific surface area and pore volume,higher dispersion of Mn and Ce species compared with MnCeO_x/TiO_2.Moreover,in situ DRIFTS was used to investigate the reaction mechanism,and the results indicate that the NH3-SCR reaction over MnCeO_x/TiO_2 and MnCeO_x/TiO_2-Al_2 O_3 takes place by both the E-R and L-H mechanisms.     

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...     

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 PdO_x structure properties on catalytic performance of Pd/Ce_(0.67)Zr_(0.33)O_2 catalyst for CO,HC and NO_x elimination

Pd/Ce_(0.67)Zr_(0.33)O_2 catalyst was pretreated in different atmosphere respectively, and characterized by CO chemical adsorption, XPS, HR-TEM, H_2-TPR, Raman, OSC and in situ DRIFTS to investigate the effect of the structure properties of PdO_x species on the catalytic performance for CO, HC and NO_x elimination. The results show that Pd/CZ catalyst pretreated in air atmosphere has higher oxidation activity of HC due to having high Pd dispersion and strong interaction between PdO_x and CZ support. Pd/CZ-H catalyst pretreated in reducing atmosphere exhibits better catalytic performance of NO_x elimination because of having relatively big Pd particle size, more Pd species in metallic state and higher concentration of oxygen vacancies. While for the Pd/CZ-RG catalyst pretreated in reactant atmosphere, strong adsorption of HC species on the surface of catalysts would lead to a part of active sites being covered, which inhibits HC and NO conversions.     

Catalytic oxidation of CO on mesoporous codoped ceria catalysts:Insights into correlation of physicochemical property and catalytic activity

Codoping approach is an appealing strategy to further improve the catalytic activity of Ce-based catalysts. In the present study,Mn and/or Cu doped ceria solid solutions MnxCuyCe_(1-x-y)O_2,Cu_xCe_(1-x)O_2,Mn_xCe_(1-x)O_2 and pure CeO_2 were prepared by CTAB-assisted hydrothermal method for CO oxidation.XRD, SEM, EDS, BET, Raman, H2-TPR, XPS and in situ DRIFTS techniques were carried out to study the physicochemical properties and to correlate them to the activity. The doped samples maintain the cubic fluorite structure of CeO_2 with high crystallinity and small crystallite size, forming Ce-based solid solutions. The obtained catalysts have large mesoporous structure with average pore size of 10-14 nm. The doped transition metal enhances the oxygen vacancies and improves reducibility of the solids. The synergistic interaction of Mn and Cu codoping induces mo re oxygen vacancies, pro moting the increase of surface adsorbed oxygen and the transfer of bulk oxygen of catalyst, thereby enhancing the catalytic activity for CO oxidation. Besides, the decomposition rate of the carbonate species which is derived from in situ DRIFTS for each catalyst can provide a measure to evaluate its catalytic activity of CO oxidation.     

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...     

Novel promoting effects of cerium on the activities of NO_x reduction by NH_3 over TiO_2-SiO_2-WO_3 monolith catalysts

A series of catalysts were prepared by doping different loadings of CeO2 over TiO2-SiO2-WO3 and used for the selective catalytic reduction of NOx by NH3. The experimental results showed that the selective catalytic reduction（SCR） performance and SO2-resistant ability of TiO2-SiO2-WO3 were greatly enhanced by the introduction of cerium. The catalyst containing 10% CeO2 showed the highest NO conversion in a wide temperature range and good N2 selectivity with broad operation temperature window at the gas hourly space velocity（GHSV） of 30000 h–1, which was a very promising catalyst for NOx abatement from diesel engine exhaust. The catalysts were characterized by X-ray diffraction（XRD）, scanning electron microscopy with energy dispersive X-ray spectroscopy（SEM-EDS）, N2 adsorption-desorption（BET） and X-ray photoelectron spectroscopy（XPS）. The characterization results showed that the bigger pore radius, higher surface atomic concentration and dispersion of Ce and the abundant adsorbed oxygen on the surface of catalyst contributed to the best NH3-SCR performance of CeO2/TiO2-SiO2-WO3 catalyst containing 10% CeO2.     

Synergistic effects of PtFe/CeO2 catalysts afford high catalytic performance in selective hydrogenation of cinnamaldehyde

Selective hydrogenation of unsaturated aldehydes remains a grand challenge in controlling chemoselectivity up to now.We synthesized a series of PtFe_x/CeO₂ catalysts,which were characterized by X-ray diffraction(XRD),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS) as well as temperature-programmed-reduction by hydrogen(H₂-TPR).The catalytic performance of PtFe_x/CeO₂,including cinnamaldehyde(CAL) conversion and sele...     

A comparative study of hydrothermal aging effect on cerium and lanthanum doped Cu/SSZ-13 catalysts for NH_3-SCR

Ce-or La-doped Cu/SSZ-13 catalysts were prepared by a hydrothermal method and Cu,Ce or La ions were incorporated through stepwise ion exchange,The catalyst activity was measured for the ammonia selective catalytic reduction reaction.The structure and composition of catalyst were characterized by using X-ray diffraction,scanning electron microscopy,inductively coupled plasma mass spectrometry solid-state NMR,NH_3-TPD techniques,and the active components were examined by XPS and XANES.The results indicate that the Ce and La doping can both completely preserve the SCR activity of Cu/SSZ-13 above 300℃,but there is also a decrease of activity below 200℃.On the other hand,Ce doping is beneficial to the formation of framework aluminum,stabilizes molecular sieve framework and Cu active sites of Cu/SSZ-13,thereby improves the catalyst hydrothermal stability.But La doping will decrease the amount of framework aluminum and Cu active sites of Cu/SSZ-13 after hydrothermally aging,even destroy zeolite CHA structure.This is quite harmful to the catalyst hydrothermal stability.     

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.     

Role of cerium dopants in MoVNbO multi-metal oxide catalysts for selective oxidation of ethane

The effect of Ce on the structure of MoVNbCeO multi-metal oxide catalysts and the performance of ethane selective oxidation was investigated. These multi-metal oxide catalysts with superior oxidizability exhibit high catalytic activity, and vanadium acts as the active center for ethane oxidation reaction. The improved catalytic activity is related to the increased V⁵⁺ content on the catalyst surface, which results from the enhanced transformation of the electrons between V and Ce. Moreover, Ce effectively promotes oxygen adsorption, activation, and mobility. And the presence of Ce can also prevent MoO₃ formation and stabilize the Mo₅O₁₄-like structure. In addition, the catalyst with a moderate amount of Ce exhibits outstanding catalytic performance. Especially, the MVN-Ce catalyst with a Ce/V ratio of 0.1 exhibits the best performance: the total selectivity of the catalyst toward C₂H₄ and CH₃COOH is the highest (72%) at the ethane conversion of 31%. Therefore, MoVNbCeO multi-metal oxides are promising candidates for selective oxidation.