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.     

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.     

Selective catalytic reduction of NOx with NH3 over core-shell Ce@W catalyst

An environmentally benign WO₃ wrapped cubic CeO₂ core–shell catalyst (Ce@W) was developed for the selective catalytic reduction of NO_x with NH₃. Compared with CeW particles prepared via the conventional co-precipitation method, this core–shell catalyst not only displays higher tolerance to SO₂ and H₂O, but also exhibits a wider activity temperature window of 250–450 °C, in which NO_x conversion and N₂ selectivity reaches 100%. The improved performance of Ce@W catalysts can be contributed to the strong interactions between CeO₂ (100) and WO₃, which generates more Ce³⁺ and surface chemisorbed oxygen. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTs) reveal that the more thermally stable Brønsted acid sites on Ce@W lead to its excellent high-temperature activity.     

Regeneration of the deactivated TiO2-ZrO2-CeO2 /ATS catalyst for NH3-SCR of NOx in glass furnace

Larger amounts of alkalis, alkali earth metals and sulfides in flue gas from glass furnace were easier to deactivate selective catalytic reduction (SCR) catalyst compared to the flue gases from other stationary sources. Catalyst regeneration has been an emerging research topic for flue gas denitrification in glass furnace. Regeneration of the deactivated TiO2-ZrO2-CeO2 /Al2TiO 5 -TiO2-SiO2 (ATS) complex phase ceramics catalysts used for NH3 -SCR of NO x in glass furnace was studied in this work. Effects of regeneration methods, including washing with different aqueous solutions and sulfuric acid, thermal regeneration, thermal reduction regeneration, and thermal regeneration with SO2 , on catalytic performance were comparatively investigated. In comparison of catalytic activities between the catalysts before and after regeneration, results showed that washing was the most effective regeneration method, and the sulfuric acid concentration of the washing solution was an important factor. Washing time directly affected catalyst regeneration efficiency and catalyst life. The regenerated TiO2-ZrO2 -CeO2 /ATS catalyst regained more than 90% NO conversion after being washed with 10 wt.% H2SO4 for 30 min.     

Extruded monolith MnOx-CeO2-TiO2 catalyst for NH3-SCR of low temperature flue gas from an industry boiler: Deactivation and recovery

The selective catalytic reduction(SCR) of NO_x with NH₃(NH₃-SCR) technology has been widely applied for reducing NO_x emissions from stationary and mobile sources.In this work,the extruded monolith MnO_x-CeO₂-TiO₂ catalyst was installed in a cement kiln for NH₃-SCR of NO_x,where the flue gas temperature was 110-140℃.It is found that the monolith catalyst is severely deactivated after operating for abou...     

Effects of different introduction methods of Ce4+ and Zr4+ on denitration performance and anti-K poisoning performance of V2O5-WO3/TiO2 catalyst

The purpose of this work is to explore the effects of the introduction methods of Ce⁴⁺ and Zr⁴⁺ on the physicochemical properties, activity, and K tolerance of V₂O₅-WO₃/TiO₂ catalyst for the selective catalytic reduction of NO_x by NH₃. Four different methods, namely pre-impregnation, post-impregnation, co-impregnation, and co-precipitation, were used to synthesize a series of V₂O₅-WO₃-TiO₂-CeO₂-ZrO₂ catalysts. The catalysts were characterized by XRD, BET, NH₃-TPD, XPS, and H₂-TPR techniques. Moreover, the activity and anti-K poisoning performance were tested by an NH₃-SCR model reaction. The results show that the introduction of Ce⁴⁺ and Zr⁴⁺ can improve the catalytic performance of V₂O₅-WO₃/TiO₂ catalyst, but the impregnation method cannot enhance the anti-K poisoning performance. Ce⁴⁺ and Zr⁴⁺ introduced by co-precipitation method can effectively improve the tolerance of K, which is mainly due to the incorporation of Ce⁴⁺ and Zr⁴⁺ into TiO₂ lattice to form a uniform TiO₂-CeO₂-ZrO₂ solid solution, resulting in the optimal surface acidity and redox performance, and reducing the decreases caused by K-poisoning. Furthermore, based on the best introduction method, we further optimized the molar ratio of Ce⁴⁺/Zr⁴⁺. It is found that the catalyst exhibits the best anti-K poisoning performance when the molar ratio of Ce⁴⁺/Zr⁴⁺ is 2:1.     

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.     

Promotion effect of H2 pretreatment on CeO2 catalyst for NH3-SCR reaction

In this study, the promotion effect of H₂ pretreatment on the SCR performance of CeO₂ catalyst was investigated based on the characterization results of XRD, H₂-TPR, Raman and in situ DRIFT techniques. Lower crystallinity, higher reducibility and surface acidity can be found on CeO₂-H catalyst. The results of DRIFT study reveal that the pretreatment of CeO₂ catalyst with H₂ can facilitate the adsorption of NH₃ and NO_x species, while the adsorbed NO_x is basically inactive in the NH₃-SCR reaction. Moreover, the reaction mechanism of the NH₃-SCR reaction over CeO₂ catalyst is not changed by H₂ pretreatment, which is mainly under the control of Eley-Rideal (E-R) mechanism. The enhanced SCR performance of CeO₂-H catalyst is mainly due to the promoted NH₃ adsorption and the subsequent facilitation of SCR reaction through E-R pathway.     

Doping effect of rare earth metal ions Sm3+, Nd3+ and Ce4+ on denitration performance of MnOx catalyst in low temperature NH3-SCR reaction

The MnXO_x catalysts(i.e.,MnSmO_x,MnNdO_x,MnCeO_x) were prepared by reverse co-precipitation method and used for NH₃-SCR reaction.It is found that MnCeO_x catalyst presents the best low tempe rature catalytic activity(higher than 90% NO_x conversion in the te mperature range from 125 to 225℃)and excellent H₂O+SO₂ resistance.In order to explore the reason for this result,the characterization of X-ray diff...     

Getting insights into gas-phase sulfation effect on catalytic performance of praseodymium oxides in NH3-SCR of NO

Sulfation treatment has been widely used to promote the catalytic performance of ceria(CeO₂) based catalysts for the selective catalytic reduction of NO by NH₃(NH₃-SCR of NO).Praseodymium oxide(PrO_x),another commonly used rare earth material with similar structural properties as CeO₂,also shows satistactory redox properties due to the facile redox cycle of Pr³⁺■Pr⁴⁺.In this work,gas phase sulfation treatment with varied...     

Hydrogen production from ammonia decomposition over Ni/CeO2 catalyst: Effect of CeO2 morphology

Ammonia(NH₃) decomposition to release CO_x-free hydrogen(H₂) over non-noble catalysts has gained increasing attention.In this study,three nanostructured CeO₂ with different morphologies,viz.rod(R).sphere(Sph),and spindle(Spi),were fabricated and served as supports for Ni/CeO₂ catalyst.The CeO₂supports are different in particle sizes,specific surface area and porosity,resulting in the formation of Ni nanoparticles with distinguished...     

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...     

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.     

Transition metal doping effect and high catalytic activity of CeO2–TiO2 for chlorinated VOCs degradation

A series of transition metals (Fe, Co, Ni, Cu, Cr and Mn)-doped CeO₂–TiO₂ catalysts were prepared by the sol–gel method and applied for the catalytic removal of 1,2-dichloroethane (DCE) as a model for chlorinated VOCs (CVOCs). The various characterization methods including X-ray diffraction (XRD), N₂ adsorption–desorption, UV-Raman, NH₃ temperature-programmed desorption (NH₃-TPD) and H₂ temperature-programmed reduction (H₂-TPR) were utilized to investigate the physicochemical properties of the catalysts. The results show that doping Fe, Co, Ni or Mn can obviously promote the activity of CeO₂–TiO₂ mixed oxides for DCE degradation, which is related to their improved texture properties, acid sites (especially for strong acidity) and low-temperature reducibility. Particularly, CeTi–Fe doped with moderate Fe exhibits excellent activity for 1,2-dichloroethane (DCE) degradation, giving a T_90% value as low as 250 °C. More importantly, only trace chlorinated byproducts were produced during the low-temperature degradation of various CVOCs (dichloromethane (DCM), trichloroethylene (TCE) and chlorobenzene (CB)) over CeTi–Fe1/9 catalyst with high durability.     

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.     

Catalytic ozonation of NH4+-N in wastewater over composite metal oxide catalyst

Large amounts of water containing-ammonium nitrogen(NH₄⁺-N)have attracted increasing attention.Catalytic ozonation technology,involving the generation of hydroxyl radical(OH)with strong oxidation ability,was originally utilized to degrade organic-containing wastewater.In this paper,Ce/MnOx composite metal oxide catalysts prepared with different preparation conditions were used to degrade wastewater containing inorganic pollutant(NH₄⁺-N).The as-prepared catalyst features were characterized using X-ray diffraction(XRD),Brunauer-Emmett-Teller method(BET),scanning electron microscopy(SEM),energy dispersive X-ray spectroscopy(EDS),Fourier transform infrared spectroscopy(FTIR),X-ray photoelectron spectroscopy(XPS)and H₂-temperature programmed reduction(H₂-TPR)techniques.The results show that the catalyst,prepared by conditions with precipitant Na₂CO₃ and Ce/Mn molar ratio 1:2 calcined at 400℃for 3 h in pH 11.0,displays the optimal performance,with the removal rate of NH₄⁺-N and selectivity to gaseous nitrogen,88.14 wt%and 53.67 wt%,respectively.The effects of several operating factors including solution pH,initial NH₄⁺-N concentrations and scavengers were evaluated.In addition,XRD patterns of catalyst with the best performance and the comparative study on decontamination of NH₄⁺-N by various processes(O₃,catalyst and catalyst/O₃)show that the primary metal oxides are CeO₂ and MnO₂ in Ce/MnOx composite metal oxide catalysts,which have a synergistic effect on the catalytic ozonation of NH₄⁺-N,and the new phase MnO₂ plays a great role.After 5 consecutive use cycles,the degradation efficiency is declined slightly,and can still achieve better than 70 wt%over 1 h reaction.Additionally,the application of catalytic ozonation for actual wastewater on the removal rate of NH₄⁺-N was investigated.Possible mechanism and degradation pathway of NH₄⁺-N were also proposed.In a word,the application of CeO₂-MnO₂ composite metal oxide catalysts in catalytic ozonation can be regarded as an effective,feasible and promising method for the treatment of NH₄⁺-N.     

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.     

Synergetic effect of thermo-photocatalytic oxidation of benzene on Pt-TiOe/Ce-MnOx

Pt-TiO2/Ce-MnOx catalysts were obtained by depositing TiO2 and platinum, respectively,on the Ce-Mn oxides prepared by co-precipitation method. The phases of CeO2 and anatase TiO2 were observed in the catalysts from X-ray diffraction (XRD) patterns. X-ray photoelectron spectroscopy (XPS) revealed that lattice oxygen and surface active oxygen were found to be the major components of O1s. The experiment results showed that the kinetic constant of thermo-photocatalysis was 7.6 times of the kinetic constant of single photocatalysis, and was 2.29 times of the kinetic constant sum of photocatalytic and thermal catalytic reaction.     

Surface exsolution and local atomic structure of amorphous CeTiOx

We made precipitated nano-ceria (～5 nm) on the surface of the catalyst by heat treatment of Ce-supersaturated amorphous CeTiO_x to improve the oxygen storage properties of CeO₂. The catalysts were prepared by sol-gel methods and TiO₂ nanoparticles were preferentially generated as a core material to form selective Ce-supersaturated structure on the catalyst surface. Reaction temperature and amount of doping element are optimized to induce selective crystallization of CeO₂. CeCe (2nd shell) bond around 0.38 nm of Ce L₃-edge extended X-ray absorption fine structure is reduced and nanostructure of precipitated ceria on the surface is observed by HREM. The catalyst is present as amorphous with precipitated nano-CeO₂ on the surface. The de-NO_x efficiency of the catalyst, which has precipitated CeO₂, improves by ～50% owing to the simultaneous reactions of the nano CeO₂ and the amorphous CeTiO_x.     

A novel ceria hollow nanosphere catalyst for low temperature NOx storage

In this work, a highly active CeO₂ catalyst with hollow nanosphere morphology for low temperature NO_x storage was prepared by a surfactant-assisted solvothermal reaction. The physicochemical properties of ceria samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ adsorption–desorption, H₂-temperature programmed reduction (H₂-TPR), X-ray photoelectron spectroscopy (XPS) and in situ diffused reflectance infrared Fourier transform spectroscopy (DRIFTS). The as-prepared CeO₂ nanosphere possesses excellent NO oxidation capacity, smaller mesopores, better reducibility and more surface Ce³⁺ content. Compared with CeO₂ with nanorod and nanoparticle morphologies, CeO₂ nanosphere shows better intrinsic low temperature NO_x trapping performance, with a wide operating temperature window (150–300 °C), high NO_x adsorption capacity (NAC, 640–745 μmol/g) and high NO_x storage capacity (NSC, 250–350 μmol/g). Two reaction pathways are speculated for NO_x adsorption on CeO₂ nanosphere, including “nitrate route” and “nitrite route”. The thermally unstable surface nitrites formed on the CeO₂ nanosphere allow ceria to release more NO_x during the desorption process. The present work provides a new ceria morphology for NO_x traps, which may become a potential excellent NO_x storage material.